7722-84-1

Basic information

• Product Name: Hydrogen peroxide
• Synonyms: albone35cg;albone50;albone50cg;albone70;albone70cg;alboneds;Dihydrogen dioxide;dihydrogendioxide
• CAS NO: 7722-84-1
• Molecular Formula: H₂O₂
• Molecular Weight: 34.01
• EINECS: 231-765-0
• Product Categories: Oxidative Stress Proteins and ReagentsSynthetic Reagents;Cell Stress;Nitric Oxide and Cell Stress;Oxidation;Peroxides;Synthetic Reagents;PeroxidesMicro/Nanoelectronics;Electronic Chemicals;Semiconductor Grade Chemicals;Analytical Reagents;Pure Reagents for Wet Digestion (Trace SELECT)Analytical/Chromatography;Trace Analysis Reagents;Atomic Absorption Spectroscopy (AAS);Digestion Reagents;Ultrapure Reagents for Wet Digestion (Trace SELECTUltra);CatalaseAnalytical Reagents for General Use;E-L, Puriss p.a. ACS;Enzyme Substrates;Puriss p.a. ACS;Substrates by Enzyme;PeroxidesEssential Chemicals;Reagent Grade;Routine Reagents;ACS GradeSynthetic Reagents;Essential Chemicals
• Mol File: 7722-84-1.mol
• Article Data: 656

Chemical Properties

• Melting Point: -33 °C
• Boiling Point: 108 °C
• Flash Point: 107°C
• Appearance: ≤10(APHA)/Solution
• Density: 1.13 g/mL at 20 °C
• Vapor Density: 1.1 (vs air)
• Vapor Pressure: 23.3 mm Hg ( 30 °C)
• Refractive Index: 1.3350
• Storage Temp.: 2-8°C
• Solubility: diethyl ether: soluble
• PKA: 11.5(at 25℃)
• Water Solubility: miscible
• Stability: Slightly unstable - will very slowly decompose. Decomposition is promoted by catalysts and heating, so store cool. Light sensiti
• Merck: 14,4798
• BRN: 3587191
• CAS DataBase Reference: Hydrogen peroxide(CAS DataBase Reference)
• NIST Chemistry Reference: Hydrogen peroxide(7722-84-1)
• EPA Substance Registry System: Hydrogen peroxide(7722-84-1)

Safety Data

• Hazard Codes: Xn,C,O
• Statements: 22-41-37/38-34-20/22-8-35-5
• Safety Statements: 26-39-45-36/37/39-28A-17-28-1/2
• RIDADR: UN 2014 5.1/PG 2
• WGK Germany: 1
• RTECS: MX0899500
• TSCA: Yes
• HazardClass: 5.1
• PackingGroup: II
• Hazardous Substances Data: 7722-84-1(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 7722-84-1 differently. You can refer to the following data:
1. Hydrogen peroxide (H2O2) in a purified form is explosive. In a dilute form in water, it is used as an antiseptic and oxidizing agent.
2. Antiinfective, topical.
3. hydrogen peroxide is a bleaching and oxidizing agent, detergent, and antiseptic. It is generally recognized as a safe preservative, germ killer, and skin bleacher in cosmetics. If used undiluted, it can cause burns of the skin and mucous membranes.
4. Hydrogen peroxide is used for bleaching silk, fabrics, feathers, and hairs; in refining oils and fats; for cleaning metals surfaces; as an antiseptic; and in rocket propulsion (90% solution). It is marketed as an aqueous solution of 3-90% by weight.
5. Synthesized hydrogen peroxide is approximately 60% H2O2 by weight and is distilled tohigher concentrations and diluted to lower concentrations for intended purposes. Food grade hydrogen peroxide comes in 35% and 50% concentrations. It is usedfor disinfecting purposes and also as an ingredient in cosmetics, shampoos, and medications.Reagent hydrogen peroxide for chemical and medical laboratories has a concentration of 30%.Standard grades of 35%, 50%, 60%, and 70% are used for industrial bleaching. Generalhousehold hydrogen peroxide is 3% H2O2 and 6% is used by beauticians for hair coloring.Very high grades such as 90% are used as oxidizers in rocket propulsion. Hydrogen peroxide has a number of environmental uses. Hydrogen peroxide has a number of environmental uses. These include water treatment, odorcontrol, oxidation of pollutants, and corrosion control. Hydrogen peroxide is used to removeiron, manganese, and hydrogen sulfide from water supplies and wastewater. The oxidation ofsubstances such as hydrogen sulfide reduces odors. Because H2O2 decomposes into oxygen andwater, it has the added advantage of lowering the biological oxygen demand of wastewater.ese include water treatment, odorcontrol, oxidation of pollutants, and corrosion control. Hydrogen peroxide is used to removeiron, manganese, and hydrogen sulfide from water supplies and wastewater. The oxidation ofsubstances such as hydrogen sulfide reduces odors. Because H2O2 decomposes into oxygen andwater, it has the added advantage of lowering the biological oxygen demand of wastewater. Hydrogen peroxide is used in chemical synthesis and can function as both an oxidizing andreducing agent. Caro’s acid (H2SO5) is made using H2O2. Peracetic acid (C2H4O3) is producedby reacting acetic acid and hydrogen peroxide and is used as a disinfectant. Solid bleachingagents such as perborates and percarbonates are made using H2O2. It is used in epoxida tionand hydroxylation reactions. Epoxidation reactions involve the breaking of double bondsin alkenes, with the carbons then bonding to the same oxygen atom to form an epoxide ring.

Description

Hydrogen peroxide (H2O2) is a strong oxidizing agent that is used extensively in industry and medicine. It is usually available as aqueous solutions in concentrations of 3, 30 or 90 percent by weight. The 3 percent solution is used as a topical antiseptic and cleansing agent, and as a constituent in mouthwashes, dentifrices and sanitary lotions; the 30 percent as an effective bleaching agent and for other industrial uses; and the 90 percent as a vigorous oxidizer of rocket fuels. The anhydrous form is a colorless, bittertasting liquid with an ozone-like odor. In the absence of stabilizing agents (e.g., phosphates, tin), hydrogen peroxide solutions are unstable and decompose upon standing, agitation, exposure to light, or heating. Hydrogen peroxide reacts vigorously with many oxidizing as well as reducing agents. Concentrated solutions are highly caustic to the skin. In addition to its effectiveness as a bleach, hydrogen peroxide has proved to be a useful antimicrobial agent. This latter property has been utilized in some countries as a preservative of milk and whey.

Chemical Properties

Colorless liquid; pure compound or 90% solution unstable; bitter taste; density 1.463 g/mL; boils at 150.2°C; freezes at –0.43°C; vapor pressure 9.9 torr at 50°C and 121.5 torr at 100°C; viscosity 1.245 centipoise at 20°C; surface tension 80.4 dyn/cm at 20°C; miscible with water in all proportions; soluble in ether; densities of 30%, 70%, and 90% H2O2 solutions are 1.1081, 1.2839 and 1.3867 g/mL, respectively, at 25°C; freezing points at these concentrations are –25.7°C, –40.3°C and –11.5°C, respectively; and their boiling points are 106.2°C, 125.5°C and 141.3°C, respectively; decomposed by many organic solvents; pKa at 25°C is 11.62.

Physical properties

Colorless liquid; pure compound or 90% solution unstable; bitter taste; den-sity 1.463 g/mL; boils at 150.2°C; freezes at -0.43°C; vapor pressure 9.9 torrat 50°C and 121.5 torr at 100°C; viscosity 1.245 centipoise at 20°C; surfacetension 80.4 dyn/cm at 20°C; miscible with water in all proportions; soluble inether; densities of 30%, 70%, and 90% H2O2solutions are 1.1081, 1.2839 and1.3867 g/mL, respectively, at 25°C; freezing points at these concentrations are-25.7°C, -40.3°C and -11.5°C, respectively; and their boiling points are106.2°C, 125.5°C and 141.3°C, respectively; decomposed by many organic sol-vents; pKaat 25°C is 11.62.

History

Hydrogen peroxide was prepared first by Thenard in 1818. It has many industrial applications. Aqueous solutions at varying concentrations are used for bleaching fabrics, silks, furs, feathers and hair; as a dough conditioner; and a bleaching and oxidizing agent in foods; for cleaning metals; as a laboratory reagent for oxidation; as an antiseptic; in sewage and wastewater treatment; and in preparation of inorganic and organic peroxides. An 80% concentrated solution is used in rocket propulsion.

Production Methods

From 1920 to 1950, the primary method of production was electrolysis. One process involved passing electric current through sulfuric acid to produce the peroxydisulfate ion (S2O8 2-), which was then hydrolyzed to H2O2: 2H2O + S2O82- (aq) 2H2SO4-(aq) + H2O2(aq).the relatively high cost of electricity of this method encouraged a search for a more economical production process. Hydrogen peroxide is currently produced on a large scale using the anthraquinone autooxidation procedure, which was developed in the 1940s. In this process, an anthraquinone, typically 2-ethyl-anthraquinone, is hydrogenated to a hydroquinone (2-ethyl-anthrahydroquinone) then reoxidized back to the anthraquinone (2-ethyl-anthraquinone) while forming hydrogen peroxide . A metal palladium or nickel catalyst is used to convert the anthraquinone to the hydroquinone, followed by autooxidation in air to generate hydrogen peroxide. The anthraquinone and hydrogen peroxide are separated; the former is recycled to repeat the process while the hydrogen peroxide is purified.

Definition

Different sources of media describe the Definition of 7722-84-1 differently. You can refer to the following data:
1. hydrogen peroxide: A colourlessor pale blue viscous unstable liquid,H2O2; r.d. 1.44; m.p. –0.41°C; b.p.150.2°C. As with water, there is considerablehydrogen bonding in theliquid, which has a high dielectricconstant. It can be made in the laboratoryby adding dilute acid to bariumperoxide at 0°C. Large quantitiesare made commercially by electrolysisof KHSO4.H2SO4 solutions. Anotherindustrial process involvescatalytic oxidation (using nickel, palladium,or platinum with an anthraquinone)of hydrogen and waterin the presence of oxygen. Hydrogenperoxide readily decomposes in lightor in the presence of metal ions togive water and oxygen. It is usuallysupplied in solutions designated byvolume strength. For example, 20-volume hydrogen peroxide wouldyield 20 volumes of oxygen per volumeof solution. Although the peroxidesare formally salts of H2O2, thecompound is essentially neutral.Thus, the acidity constant of the ionizationH2O2 + H2O ?H3O+ + HO2–is 1.5 × 10-12 mol dm-3. It is a strongoxidizing agent, hence its use as amild antiseptic and as a bleachingagent for cloth, hair, etc. It has alsobeen used as an oxidant in rocketfuels.
2. ChEBI: An inorganic peroxide consisting of two hydroxy groups joined by a covalent oxygen-oxygen single bond.

Preparation

Hydrogen peroxide is commercially produced by autooxidation of ethyl anthraquinol in a solvent such as toluene or ethylbenzene. The product ethyl anthraquinone is reduced by hydrogen over supported nickel or platinum catalyst to regenerate back the starting material, ethyl anthraquinol for a continuous production of H2O2. The reaction steps are: Hydrogen peroxide may also be made by heating 2-propanol with oxygen at 100°C under 10 to 20 atm pressure: (CH3)2CHOH (CH3)2C(OH)OOH → CH3COCH3 + H2O2 Vapor phase partial oxidation of hydrocarbons also yield H2O2. However, several by-products are generated, the separations of which make the process difficult and uneconomical. Hydrogen peroxide may also be prepared by treating barium peroxide with dilute sulfuric acid: BaO2 + 2H2SO4 → H2O2 + BaSO4 Another preparative method involves electrolytic conversion of aqueous sulfuric acid to peroxydisulfate followed by hydrolysis to H2O2 (Weissenstein process). The reaction steps are as follows: 2H2SO4 → H2S2O8 + H2 H2SO5 + H2O → H2SO4 + H2SO5 H2SO5 + H2O → H2O2 + H2SO4 An earlier method, which currently is no longer practiced commercially, involved oxidation of phenyl hydrazine: Hydrogen peroxide obtained this way may contain many impurities, depending on the process used. Such impurities are removed by ion exchange, solvent extraction, and distillation. Dilute solutions of H2O2 may be purified and concentrated by fractional distillation at reduced pressures.

Reactions

Hydrogen peroxide reacts with many compounds, such as borates, carbonates, pyrophosphates, sulfates, silicates, and a variety of organic carboxylic acids, esters, and anhydrides to give peroxy compounds or peroxyhydrates. A number of these compounds are stable solids that hydrolyze readily to give hydrogen peroxide in solution.

General Description

A colorless liquid dissolved in water. Vapors may irritate the eyes and mucous membranes. May violently decompose on contact with most common metals and their compounds. Contact with combustible material may result in spontaneous ignition. Corrosive to tissue. Under exposure to fire or heat containers may violently rupture due to decomposition. Used to bleach textiles and wood pulp, in chemical manufacturing, food processing, and in water purification.

Air & Water Reactions

Water soluble.

Reactivity Profile

The hazards associated with the use of HYDROGEN PEROXIDE(especially highly concentrated solutions) are well documented. There is a release of enough energy during the catalytic decomposition of 65% peroxide to evaporate all water and ignite nearby combustible materials. Most cellulose materials contain enough catalyst to cause spontaneous ignition with 90% peroxide. Contamination of concentrated peroxide causes the possibility of explosion. Readily oxidizable materials, or alkaline substances containing heavy metals may react violently. Solvents(acetone, ethanol, glycerol) will detonate on mixture with peroxide of over 30% concentration, the violence increasing with concentration. Concentrated peroxide may decompose violently in contact with iron, copper, chromium, and most other metals or their salts, and dust(which frequently contain rust). During concentration under vacuum of aqueous or of aqueous-alcoholic solutions of hydrogen peroxide, violent explosions occurred when the concentration was sufficiently high(>90%), [Bretherick 2nd ed., 1979]. Hydrogen selenide and hydrogen peroxide undergo a very rapid decomposition, [Mellor 1:941(1946-1947)].

Hazard

Hydrogen peroxide is a strong oxidizing agent. Concentrated solutions, even a 30% aqueous solution, should be handled carefully. The compound decomposes violently in the presence of trace impurities. Inhibitors are, therefore, added at trace levels to prevent decomposition. Explosion can occur when concentrated solutions are heated or brought in contact with a number of organic substances that are readily oxidizable or that form organic peroxides, such as alcohols, aldehydes, ketones, anhydrides, and carboxylic acids (Patnaik, P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd ed. New York: John Wiley & Sons). Also, reactions with metals, metal alloys, a number of metal salts and oxides, and concentrated mineral acids can proceed to explosive violence.

Health Hazard

Different sources of media describe the Health Hazard of 7722-84-1 differently. You can refer to the following data:
1. Concentrated solutions of hydrogen peroxide are very caustic and can cause burns of skin and mucous membranes. Exposure to its vapors can produce body irritation, lacrimation, sneezing, and bleaching of hair. A dose of 500 mg/kg by dermal route caused convulsions and deaths in rabbits. The oral LD50 value for 90% peroxide solution in mice is 2000 mg/kg.Oral administration of hydrogen peroxide produced tumors in gastrointestinal tract in mice. There is limited evidence of carcinogenicity in animals. Cancercausing effects of hydrogen peroxide in humans are unknown. Padma and coworkers (1989) reported the promoting effect of hydrogen peroxide on tobacco-specific Nnitrosoamines in inducing tumors in the lung, liver, stomach, and cheek pouch in Syrian golden hamsters and mice. The incidence of cheek pouch tumors increased when peroxide was administered concurrently or applied for a long period after a low initiator dose of N-nitrosamines. .
2. Contact with aqueous concentrations of less than 50% cause skin irritation, but more concentrated solutions of H202 are corrosive to the skin. At greater than 10% concentration, hydrogen peroxide is corrosive to the eyes and can cause severe irreversible damage and possibly blindness. Hydrogen peroxide is moderately toxic by ingestion and slightly toxic by inhalation. This substance is not considered to have adequate warning properties. Hydrogen peroxide has not been found to be carcinogenic in humans. Repeated inhalation exposures produced nasal discharge, bleached hair, and respiratory tract congestion, with some deaths occurring in rats and mice exposed to concentrations greater than 67 ppm

Fire Hazard

Hydrogen peroxide is not flammable, but concentrated solutions may undergo violent decomposition in the presence of trace impurities or upon heating

Flammability and Explosibility

Hydrogen peroxide is not flammable, but concentrated solutions may undergo violent decomposition in the presence of trace impurities or upon heating.

Contact allergens

Hydrogen peroxide is an oxidizing agent used as a topi- cal antiseptic, and as part of permanent hair-dyes and color-removing preparations, and as a neutralizing agent in permanent waving. The concentration of the hydrogen peroxyde solution is expressed in volume or percentage: Ten volumes correspond to 3%. It is an irritant.

Toxicology

Hydrogen peroxide is used as an agent to reduce the number of bacteria in dairy products or other foodstuffs. In the dairy industry, hydrogen peroxide also has been used as a substitute for heat pasteurization in the treatment of milk and as a direct preservative in keeping the quality of the milk. In Japan, it has been used as a preservative for fish-paste products. Hydrogen peroxide also has a bleaching effect. The use of highly pure hydrogen peroxide in manufactured cheese has been approved by the United States Food and Drug Administration (industrial grade hydrogen peroxide is usually a 3–35% aqueous solution; a commercial home product is a 3% aqueous solution). Acute toxicities (LD50) of hydrogen peroxide for rats are 700 mg/kg/b.w. and 21 mg/kg/b.w. by subcutaneous injection and intravenous injection, respectively. When large amounts of hydrogen peroxide were injected directly into the stomachs of rats, weight and blood protein concentrations were changed slightly. When hydrogen peroxide was mixed with feed, however, no abnormalities were observed. The use of bactericides has been limited due to their toxicity to humans, and only hydrogen peroxide currently is recognized for use.

Carcinogenicity

Chronic studies in mice found adenomas and carcinomas of the duodenum after oral administration. The IARC has determined that there is limited evidence in experimental animals for the carcinogenicity of hydrogen peroxide and inadequate evidence in humans.

storage

Use extreme care when carrying out reactions with hydrogen peroxide because of the fire and explosion potential (immediate or delayed). The use of safety shields is advisable, and is essential for experiments involving concentrated (>50%) solutions of hydrogen peroxide. Sealed containers of hydrogen peroxide can build up dangerous pressures of oxygen, owing to slow decomposition.

Purification Methods

The 30% material has been steam distilled using distilled water. Gross and Taylor [J Am Chem Soc 72 2075 1950] made 90% H2O2 approximately 0.001M in NaOH and then distilled it under its own vapour pressure, keeping the temperature below 40o, the receiver being cooled with a Dry-ice/isopropyl alcohol slush. The 98% material has been rendered anhydrous by repeated fractional crystallisation in all-quartz vessels. EXPLOSIVE IN CONTACT WITH ORGANIC MATERIAL.

Incompatibilities

Contact with many organic compounds can lead to immediate fires or violent explosions (consult Bretherick for references and examples). Hydrogen peroxide reacts with certain organic functional groups (ethers, acetals, etc.) to form peroxides, which may explode upon concentration. Reaction with acetone generates explosive cyclic dimeric and trimeric peroxides. Explosions may also occur on exposure of hydrogen peroxide to metals such as sodium, potassium, magnesium, copper, iron, and nickel.

Waste Disposal

Excess hydrogen peroxide and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines. For more information on disposal procedures, see Chapter 7 of this volume.

InChI:InChI=1/H2O2/c1-2/h1-2H

Synthetic route

1,2-cyclooctene (931-88-4, 22770-27-0, 3958-30-3) → 1,8-octanedial (638-54-0) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With oxygen; ozone In acetic acid at 16℃;	A n/a B 100%
With oxygen; ozone; Fe-(ll)-Kat In acetic acid at 16℃;	A n/a B 74%
With oxygen; ozone; Mn-(ll)-Kat In acetic acid at 16℃;	A n/a B 71%

oxygen (80937-33-3) + benzoic acid (65-85-0) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With (CH3(CH2)3)4NClO4; 1-methylimidazole In dichloromethane Electrolysis; electrolysis (10-30 min) of O2 in CH2Cl2-0.1 M Bu4NClO4 soln. in presence of 0.1 M benzoic acid and 1-methylimidazole, working electrode: polymer-coated (poly-(Ru(vbpy)3)(2+)) glassy-carbon, reference electrode: Ag/Ag(1+), potential -1.3 and -1.1 V; extn. with distd. H2O, colorimetric analysis;	100%
With (CH3(CH2)3)4NClO4 In dichloromethane Electrolysis; electrolysis (10-30 min) of O2 in CH2Cl2-0.1 M Bu4NClO4 soln. in presence of 0.1 M benzoic acid, working electrode: polymer-coated (poly-(Ru(vbpy)3)(2+)) glassy-carbon, reference electrode: Ag/Ag(1+), potential -1.3 V; extn. with distd. H2O, colorimetric analysis;	99%
With (CH3(CH2)3)4NClO4; 1-methylimidazole In dichloromethane Electrolysis; electrolysis (10-30 min) of O2 in CH2Cl2-0.1 M Bu4NClO4 soln. in presence of 0.1 M benzoic acid and 1-methylimidazole, working electrode: polymer-coated (poly-(Ru(vbpy)3)(2+)) glassy-carbon, reference electrode: Ag/Ag(1+), potential -1.0 V; extn. with distd. H2O, colorimetric analysis;	97%

oxygen (80937-33-3) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With perchloric acid In water at 20℃; Reagent/catalyst; Electrochemical reaction;	100%
With N21,N22-dimethyl-2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetrakis(4-trifluoromethylphenyl)porphyrin; trifluoroacetic acid In water; acetonitrile at 20℃; for 0.5h; Catalytic behavior; Solvent; Reagent/catalyst; Concentration;	100%
With diphenyl hydrazine In ethanol 0°C;;	97%

tetra-n-butylammonium hydroxide + tris(benzene-1,2-dithiolate)molybdenum(VI) (10507-76-3) → tris(benzene-1,2-dithiolato)molybdenum(IV)(2-) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In tetrahydrofuran Kinetics; not isolated, detected by UV;	A 100% B n/a

tetra-n-butylammonium hydroxide + tris(benzene-1,2-dithiolate)molybdenum(VI) (10507-76-3) → tris(benzene-1,2-dithiolato)molybdenum(V)(1-) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In tetrahydrofuran Kinetics; not isolated, detected by UV;	A 100% B n/a

perchloric acid (7601-90-3) + oxygen (80937-33-3) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With C57H42CoFe3N4 at 20℃; Catalytic behavior; Reagent/catalyst; Electrochemical reaction;	100%
With catalyst: Ba/carbon In perchloric acid aq. HClO4; Electrochem. Process; electroreduced on Ba/carbon in 0.1 M HClO4 (1 bar, 21+/-0.5°C, 1.2 V vs. RHE);
With catalyst: Ce/carbon In perchloric acid aq. HClO4; Electrochem. Process; electroreduced on Ce/carbon in 0.1 M HClO4 (1 bar, 21+/-0.5°C, 1.2 V vs. RHE);

1,4-bis(trimethylsilyl)-2-methyl-1,4-cyclohexadiene (18406-93-4) + oxygen (80937-33-3) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
In acetonitrile at 20℃; under 760.051 Torr; for 16h; Solvent;	98%

dipotassium peroxodisulfate + sulfuric acid (7664-93-9) + water (7732-18-5) → potassium hydrogensulfate (7646-93-7) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In sulfuric acid hydrolysis by heating; simultaneous distn. (by H2O vapor);; distn.; 40-60% aq. soln. of H2O2;;	A n/a B 95%
In sulfuric acid aq. H2SO4; hydrolysis by heating; simultaneous distn. (by H2O vapor);; distn.; 40-60% aq. soln. of H2O2;;	A n/a B 95%
In sulfuric acid hydrolysis by heating; simultaneous distn. (by H2O vapor);; distn.;;	A n/a B 92%

(bis(2-pyridylmethyl)(2-quinolylmethyl)amine)(triphenylphosphino)copper(I) hexafluorophosphate * 0.25 diethylether → (μ-1,2-peroxo)bis(bis(2-pyridylmethyl)(2-quinolylmethyl)amine)copper(II) bis(hexafluorophosphate) + dihydrogen peroxide (7722-84-1)

Conditions

Yield

With HBF4*Et2O In further solvent(s) HBF4*Et2O is added to a soln. of copper dioxygen compound in propionitrile at -80°C, mixt. is stirred for 15 min;; ether is added, ppt. is allowed to settle, supernatant is transferred toa soln. of KI in distd. H2O and EtCOOH, ppt. is washed (ether) and supernatant is transferred again, mixt. containing KI is stirred for 15 min at room temp. and titrated (Na2S2O3);

A 94% B n/a

oxygen (80937-33-3) + potassium hydroxide → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With N-doped carbon nanoflowers Reagent/catalyst; Electrochemical reaction;	94%
In water Electrochemical reaction;	41.5%
With nitrogen doped porous carbon nanoparticle derived from zeolitic imidazolate framework Reagent/catalyst; Electrochemical reaction;	14%

hydrogen (1333-74-0) + oxygen (80937-33-3) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
In sulfuric acid Electrolysis; oxyhydrogen gas-cel; electrolyt: 0.5 n H2SO4; electrode spaces separated by a clay-diaphragma; electrodes: platinated Pt calcinated for 2 1/2 h at 1200-1400°C; 1 mA current strength; reaction time: 45 min; ice cooling;;	93.5%
In sulfuric acid aq. H2SO4; Electrolysis; oxyhydrogen gas-cel; electrolyt: 0.5 n H2SO4; electrode spaces separated by a clay-diaphragma; electrodes: platinated Pt calcinated for 2 1/2 h at 1200-1400°C; 1 mA current strength; reaction time: 45 min; ice cooling;;	93.5%
In sulfuric acid Electrolysis; oxyhydrogen gas-cel; electrolyt: 0.5 n H2SO4; electrode spaces separated by a clay-diaphragma; electrodes: platinated Pt calcinated for 2 1/2 h at 1200-1400°C; 2 mA current strength; reaction time: 45 min; ice cooling;;	86.3%

sulfuric acid monohydrate (50981-12-9, 10193-30-3) + ammonium sulfate-hydrogen peroxide(1/1) → caro's acid (7722-86-3) + dihydrogen peroxide (7722-84-1) + Marshall's acid (13445-49-3)

Conditions	Yield
without water, -10°C;	A 93.5% B 1.4% C 5.1%
without water, -10°C;	A 93.5% B 1.4% C 5.1%

sodium chloride (7647-14-5) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
In water Electrolysis; spark electrolysis of a 0.1n NaCl solution below 10°C, 40 mA under O2;;	90%
In water Electrolysis; spark electrolysis of a 0.1n NaCl solution below 10°C, 40 mA under O2;;	90%
In water Electrolysis; spark electrolysis of a 0.1n NaCl solution below 10°C, 40 mA under H2;;	80%
In water Electrolysis; spark electrolysis of a 0.1n NaCl solution below 10°C, 40 mA under H2;;	80%

(bis(2-quinolylmethyl)(2-pyridylmethyl)amine)(triphenylphosphino)copper(I) hexafluorophosphate * 0.25 diethylether → (bis(2-quinolylmethyl)(2-pyridylmethyl)amine)(triphenylphosphino)copper(I) perchlorate (155311-10-7) + dihydrogen peroxide (7722-84-1)

Conditions

Yield

With HBF4*Et2O In further solvent(s) HBF4*Et2O is added to a soln. of copper dioxygen compound in propionitrile at -80°C, mixt. is stirred for 15 min; ether is added, ppt. is allowed to settle, supernatant is transferred toa soln. of KI in distd. H2O and EtCOOH, ppt. is washed (ether) and supernatant is transferred again, mixt. containing KI is stirred for 15 min at room temp. and titrated (Na2S2O3);

A 89% B n/a

hexafluorophosphoric acid + {Cu2(XYL-O)(O2)}(1+) → C36H40Cu2N6O3(2+) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In diethyl ether; dichloromethane to a soln. of Cu-complex in CH2Cl2 at -80°C under Ar (generated in situ from (((C5H4NCH2CH2)2NCH2)2(C6H3O)Cu2)PF6 and O2) was added 10 equiv. HPF6/Et2O (purple soln. instantly turned blue), mixt. stirred 15 min; addn. Et2O, pptn., washed (ether);	A n/a B 88%

{{(((2-pyridyl)CH2CH2)2NCH2)2C6H3O}(peroxo)dicopper(II)}(1+) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With HBF4 or HPF6 React. with excess HBF4 or HPF6.;	88%

hydrogenchloride (7647-01-0) + [RhCl(O2)(2,6-(C(Me)=NiPr)2C5H3N)] (187034-69-1) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
In water detd. by iodometry;	88%

hydrogenchloride (7647-01-0) + [(6-t-butyl-phenyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine)Cu(I)]B(C6F5)4 (943218-68-6) + oxygen (80937-33-3) → [(6-t-butyl-phenyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine)Cu(II)Cl]2(B(C6F5)4)2 + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In diethyl ether under Ar; O2 bubbled through soln. of Cu complex in Et2O at -80°Cfor 10 s; excess O2 removed; HCl in Et2O added at -80°C; stirred for 30 min; warmed to room temp.; distd. H2O added; stirred at room temp. for 1 h; Et2O layer washed with pentane; ppt. recrystd. from THF-pentane; vac. dried; elem. anal.;	A 85% B 80%

((tris{(2-pyridyl)methyl}amine)Cu(II))2O2(PF6)2 → tris{(2-pyridyl)methyl}amineCu(II)(CH3CN)(PF6)2 + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With 2HPF6*Et2O -80°C;;	A 77% B 81%

water (7732-18-5) → dihydrogen peroxide (7722-84-1) + oxygen (80937-33-3)

Conditions	Yield
With sodium persulfate; tris(bipyridine)ruthenium(II) dichloride hexahydrate In aq. buffer for 2h; pH=10; pH-value; Irradiation; Inert atmosphere; Darkness;	A 8.8% B 80%
With anthracene; cerium(IV) In sulfuric acid Electrochem. Process; the discharge of electrochemically generated holes at an anthracene/water interface at 400 μA cm**-2 in 0.28 M Ce(4+) in 12 M H2SO4;
With air; carbon nanodots-Co3O4-Fe2O3 photoanode pH=13.6; Irradiation; Electrochemical reaction;
With tetrakis(N-methy.4-pyridyl) porphyrin copper tetrakis(trifluoromethanesulfonate) In aq. phosphate buffer pH=7; Electrolysis;

Pb(OH)3(1-)*Na(1+)=NaPb(OH)3 → sodium hexahydroxoplumbate(IV) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With oxygen In sodium hydroxide Irradiation (UV/VIS); photolysis (254 nm) of an oxygen-satd. soln. of Pb compd. in aq. NaOH at room temp. (continuous stream of O2); not isolated; UV spect.;	A 80% B >1

{Cu2(((C5H4NCH2CH2)2N)2CH2C6H3O)(O2)}(1+)*PF6(1-)={Cu2(((C5H4NCH2CH2)2N)2CH2C6H3O)(O2)}PF6 → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With H(1+) In not given protonation;;	80%

3,5-Di-tert-butylcatechol (1020-31-1) → 3,5-di-tert-butyl-o-benzoquinone (3383-21-9) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With [(6-chloro-N2,N2,N4,N4-tetrakis(pyridin-2-ylmethyl)-1,3,5-triazine-2,4-diamine)Cu(II)(-OH)2Cu(II)].(ClO4)2; oxygen In methanol at 25℃; pH=6; Kinetics; Mechanism; pH-value;	A n/a B 78%
With [CoII(3,5-ditert-butylsemiquinonate)(hydrotris(3,5-dimethylpyrazolyl)borate)]; oxygen In toluene at 39.84℃; under 760.051 Torr; for 24h; pH=4.4; Inert atmosphere;
With [Cu{(5-pyrazinyl)tetrazolate}(1,10-phenanthroline)2](NO3)0.5(N3)0.5·2(H2O); oxygen In methanol at 25℃; for 0.75h; Catalytic behavior; Kinetics; Mechanism;

water (7732-18-5) + oxygen (80937-33-3) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With [Cu(N,N-bis(2-pyridylmethyl)amine)](BF4)2 at 24.84℃; pH=6.7; Catalytic behavior; Reagent/catalyst; Electrolysis;	77%
With [Cu(N,N-bis(2-pyridylmethyl)amine)](BF4)2 at 24.84℃; for 0.0194444h; pH=6.7; Catalytic behavior; Reagent/catalyst; Electrolysis;	67%
With NiFe-layered double hydroxide derived mixed metal oxide(at)carbon nitride for 1.5h; pH=3; Kinetics; Reagent/catalyst; Irradiation;	63%

(2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl)Ir(acetate)(OOH) (1579297-38-3) → (2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl)Ir(acetate)(H) (1423875-77-7) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With sulfuric acid; oxygen at 20℃; under 2280.15 Torr; Inert atmosphere;	A n/a B 77%

{((C3H2NNCH3(CH3))3Cu)2O2}(2+) → dihydrogen peroxide (7722-84-1)

Conditions	Yield
With HPF6*Et2O In dichloromethane react. with an excess of acid; further unidentified Cu(II) products; detn. by iodometric titration;	75%

1,1-Diphenylmethanol (91-01-0) → benzophenone (119-61-9) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With N-hydroxyphthalimide; oxygen In ethyl acetate at 75℃; under 7600.51 Torr; for 12h; Temperature; Solvent; Reagent/catalyst; Pressure; Autoclave; Industrial scale;	A 75% B 57%

[(bathocuproine)Pd(O2)] (358625-60-2) + acetic acid (64-19-7) → (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)palladium(II) acetate (152506-88-2) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In dichloromethane-d2 mixing palladium complex with acetic acid in CD2Cl2 in NMR tube for 5 min; detected by NMR;	A n/a B 73%

[(bathocuproine)Pd(O2)] (358625-60-2) + sulfuric acid (7664-93-9) → (C6H5)2(CH3)2C6H2(C3HN)2*Pd(2+)*SO4(2-)=(C6H5)2(CH3)2C6H2(C3HN)2PdSO4 (358625-80-6) + dihydrogen peroxide (7722-84-1)

Conditions	Yield
In not given	A n/a B 73%

Co(II) tetra(4-NN'N''-trimethylanilinium)porphyrin chloride + oxygen (80937-33-3) → Co(III) tetra(4-NN'N''-trimethylanilinium)porphyrin chloride + dihydrogen peroxide (7722-84-1)

Conditions	Yield
With hydrogen cation In water Kinetics; Electrochem. Process; overvoltage of O2 reduction and H2O2 yield (catalytic effect) dependingon pH of soln. (1 - 8); cyclic voltammetry; voltammetry on glassy carbon rotating ring - disc electrode;	A n/a B 70%

dihydrogen peroxide (7722-84-1) → peroxomonophosphoric acid (13598-52-2)

Conditions	Yield
In tetrachloromethane; water byproducts: H3PO4; to suspn. of P2O5 in CCl4 added aq. H2O2 (70 wt %) dropwise (mole ratio >0.9) at 2°C under stirring, monitoring of temp., stirred for 2 h; aq. phase sepd., CCl4 layer extd. (deionized H2O), combined aq. solns.;	100%
In tetrachloromethane; water byproducts: H3PO4; to suspn. of P2O5 in CCl4 added aq. H2O2 (90 wt %) dropwise (mole ratio >0.9) at 2°C under stirring, monitoring of temp., stirred for 2 h; aq. phase sepd., CCl4 layer extd. (deionized H2O), combined aq. solns.;	99%
In tetrachloromethane; water at 0℃; for 3h;

dihydrogen peroxide (7722-84-1) + (S)-methyl 2-benzyloxy-4-methylpentanoate (108061-34-3) → (S)-4-methyl-2-(phenylmethoxy)valeric acid (108061-23-0)

Conditions	Yield
With hydrogenchloride In methanol; water	100%
With hydrogenchloride In methanol; water	100%

dihydrogen peroxide (7722-84-1) → hydroxyl (3352-57-6)

Conditions	Yield
With nitrogen In gas Kinetics; very rapid react. of metastable excited state N2 in Ar with H2O2 in discharge-flow apparatus, total gas pressure: 1-5 Torr; not isolated, detected by fluorescence spect.;	100%
In gas Irradiation (UV/VIS); OH produced by pulsed photolysis of H2O2 at 248 nm (KrF excimer laser);
iron(III) In water Kinetics; catalitic decompn. of H2O2 was studied; catalyst: Fe(3+)-ion; spectrophotometry;

(ethene)[N,N,N-tris(2-pyridylmethyl-κN)amine-κN]rhodium(I) hexafluorophosphate (198962-37-7) + dihydrogen peroxide (7722-84-1) → Rh(N(CH2C5H4N)3)(C2H4O)(1+)*PF6(1-)*1.5H2O=[Rh(N(CH2C5H4N)3)(C2H4O)]PF6*1.5H2O

Conditions	Yield
In methanol N2-atmosphere; addn. of 35% aq. H2O2 to Rh-complex, stirring at -10°C for 1 h; pptn. on Et2O addn., collection (filtration), washing (Et2O), drying (vac.); elem. anal.;	100%

Rh(C6H12(NCH3)3)(C8H12)(1+)*PF6(1-)=[Rh(C6H12(NCH3)3)(C8H12)]PF6 (198962-21-9) + dihydrogen peroxide (7722-84-1) → Rh(C6H12(NCH3)3)(C8H12O)(1+)*PF6(1-)=[Rh(C6H12(NCH3)3)(C8H12O)]PF6 (198962-27-5)

Conditions	Yield
In methanol N2-atmosphere; addn. of 35% aq. H2O2 to Rh-complex, stirring at room temp. for 1 h; pptn. on Et2O addn., collection (filtration), washing (Et2O), drying (vac.); elem. anal.;	100%

C22H17BF2N2S + dihydrogen peroxide (7722-84-1) → C22H17BF2N2OS

Conditions	Yield
With acetic acid In chloroform at 20℃; for 12h; Inert atmosphere; Cooling with ice;	100%

(1R,2R)-[cyclohexane-N,N'-diamine](ethanedioato-O,O')platinum(II) (61825-94-3) + water (7732-18-5) + dihydrogen peroxide (7722-84-1) → (SP-4-2)-(trans-R,R-cyclohexane-1,2-diamine)dihydroxo(oxalato) platinum(IV)

Conditions	Yield
at 20℃; for 24h; Darkness;	100%
at 20℃; under 760.051 Torr; Darkness;

borax + dihydrogen peroxide (7722-84-1) + sodium hydroxide (1310-73-2) → sodium perborate hexahydrate

Conditions	Yield
In water a soln.of H2O2 in anthraquinone (from the prepn. of H2O2 by the anthraquinone-method) is stirred with an aq. soln. of borax-NaOH at 30°C,to the formed aq. phase NaOH is added;; isoln. from the aq. phase and mother liqour;;	99.8%
In water a soln.of H2O2 in anthraquinone (from the prepn. of H2O2 by the anthraquinone-method) is stirred with an aq. soln. of borax-NaOH at 30°C,to the formed aq. phase NaOH is added;; isoln. from the aq. phase and mother liqour;;	99.8%
With florisil In water 15 kg MgSiO3 and 107 kg of H2O2 (in form of 20, 30 or 40weight% H2O2-soln.) are added to 1263 l of a soln. (15°C) containing 139 kg NaOH and 665 kg borax; further addition of H2O2 (equal amount) at 20°C and slow cooling down to 0°C;; separation and drying of the pptd. salt;;

borax + water (7732-18-5) + dihydrogen peroxide (7722-84-1) + sodium hydroxide (1310-73-2) → sodium monoborate peroxohydrate trihydrate

Conditions	Yield
In water stirring H2O2 (from anthraquinone process) in anthraquinone with aq. borax-NaOH-soln. at 30°C, addn. of NaOH to the aq. layer containing Na-perborate, borax and H2O2, pptn.;;	99.8%
In water stirring H2O2 (from anthraquinone process) in anthraquinone with aq. borax-NaOH-soln. at 30°C, addn. of NaOH to the aq. layer containing Na-perborate, borax and H2O2, pptn.;;	99.8%
In water formation of a NaBO2-soln. from borax and NaOH, treatment with H2O2-vapor at 30-35°C, apparatus described;;

oxalato((S,S,S)-spiro[4,4]nonane-1,6-diamine)platinum(II) + dihydrogen peroxide (7722-84-1) → (dihydroxy)malonato((S,S,S)-spiro[4,4]nonane-1,6-diamine)platinum(IV)

Conditions	Yield
In water at 70℃; for 2h;	99.6%

rhenium + tetrabutylammomium bromide (1643-19-2) + dihydrogen peroxide (7722-84-1) → tetrabutylammonium perrhenate

Conditions	Yield
With aq. NH3 In water add. of 30 % aq. H2O2 and aq. NH3 to Re powder, stirring (room temp., 1 h), addn. of further H2O2 until a clear sol. is obtained, then boiling to destroy excess H2O2, addn. of aq. NBu4Br; filtration, recrystn. (MeOH); elem. anal.;	99%

dihydrogen peroxide (7722-84-1) + tantalum pentachloride (7721-01-9) + potassium hydroxide → 3K(1+)*[Ta(O2)4](3-)=K3[Ta(O2)4]

Conditions	Yield
In methanol TaCl5 and H2O2 stirred in ice-water bath, KOH added, MeOH added, cooled to 5-8°C, MeOH added; filtered, washed with MeOH, dried in air for 45 min to 1 h;	99%

[(η6-p-cymene)RuCl2(η1-bis(diphenylphosphino)methane)] (88635-40-9) + dihydrogen peroxide (7722-84-1) → [(η(6)-cymene)RuCl2(η(1)-Ph2PCH2P(O)Ph2)] (240803-86-5)

Conditions	Yield
In tetrahydrofuran Ru complex treated with H2O2 in THF;	99%

cis-dichloro[η(2)-cis,cis-1,3,5-tris(diphenylphosphino)-1,3,5-tris-(methoxymethyl)cyclohexane]platinum(II) + dihydrogen peroxide (7722-84-1) → cis-dichloro[η(2)-cis,cis-1,3-bis(diphenylphosphino)-5-(diphenylphosphinyl)-1,3,5-tris-(methoxymethyl)cyclohexane]platinum(II)

Conditions	Yield
In dichloromethane Ar-atmosphere; slight excess of aq. H2O2, stirring (room temp., 2 h); concn., pptn. on pentane addn., collection (filtration), washing (pentane), drying (reduced pressure); elem. anal.;	99%

ammonium hexafluorophosphate + iron(II) chloride tetrahydrate + dihydrogen peroxide (7722-84-1) + 4'-diphenylphosphino-2,2':6',2''-terpyridine → Fe(C27H20N3OP)2(2+)*2PF6(1-)*3H2O = [Fe(C27H20N3OP)2](PF6)2*3H2O

Conditions	Yield
In ethanol; water (N2); refluxing the Fe salt and ligand in EtOH for 2 h, stirring (room temp., 60 h), addn. of aq. H2O2 (1 h), addn. of aq. NH4PF6; filtration (Celite), washing (H2O), dissoln. (MeCN), removal of solvent (vac.); elem. anal.;	99%

(Co(PyAS)2)Cl*2MeOH + dihydrogen peroxide (7722-84-1) → (Co(PyASO2)(PyPepSO2))

Conditions	Yield
In methanol; water 30 % H2O2 was added slowly to soln. (Co(PyAS)2)Cl in MeOH and stired in air for 2 days; solid was collected and dried under vac.;	99%

1,1'-diphenylphosphinooctamethylferrocene (211688-02-7) + dihydrogen peroxide (7722-84-1) → Fe(1,2-bis(diphenylphosphinoxide)-3,4,5-trimethylcyclopentadienyl)2 (211688-09-4)

Conditions	Yield
In dichloromethane Ar-atmosphere; addn. of 15 drops of 30% H2O2 to Fe-complex soln., stirring for 30 min; washing (H2O), drying of org. layer (MgSO4), solvent removal, recrystn. (CH2Cl2/pentane); elem. anal.;	99%

Upstream product

• 89603-32-7 5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-ol 
• 534-15-6 1,1-dimethoxyethane 
• 17088-37-8 acetone peroxide 
• 7664-93-9 sulfuric acid 
• 71-43-2 benzene 
• 50-81-7 ascorbic acid 
• 7732-18-5 water 
• 76-32-4 camphoric anhydride 
• 78-94-4 methyl vinyl ketone 
• 56-81-5 glycerol 
• 74-86-2 acetylene 
• 127-17-3 2-oxo-propionic acid 
• 121-44-8 triethylamine 
• 109-89-7 diethylamine 

Downstream Products

• 142-08-5 2-hydroxypyridin 
• 18368-71-3 4-methyl-2-nitropyridine 
• 1074-38-0 5-methyl-2-nitropyridine 
• 626-48-2 6-Methyluracil 
• 64-18-6 formic acid 
• 124-04-9 Adipic acid 
• 1504-06-9 3-methylindolin-2-one 
• 100047-40-3 4-methyl-2-nitro-pyridine-1-oxide 
• 645-93-2 ammelide 
• 56241-09-9 4-chloro-isoquinolin-1-ol 
• 91872-08-1 2,4,6-trichloro-[3]pyridylamine 
• 577-85-5 3-hydroxyflavone 
• 719-54-0 10-methyl-9, 10-dihydro-9-acridinone 
• 85-52-9 2-Benzoylbenzoic acid 

Relevant articles and documents

Kinetics and mechanism of O-O bond cleavage in the reaction of [Ru III(edta)(H2O)]- with hydroperoxides in aqueous solution

The reactions of [RuIII(edta)(H2O)]- (1) (edta = ethylenediaminetetraacetate) with tert-butylhydroperoxide ( tBuOOH) and potassium hydrogenpersulfate (KHSO5) were studied kinetically as a function of oxidant concentration and temperature (10-30 °C) at a fixed pH of 6.1 using stopped-flow techniques. Kinetic results were analyzed by using global kinetic analysis techniques. The reaction was found to consist of two steps involving the rapid formation of a [Ru III(edta)(OOR)]2- intermediate, which subsequently undergoes heterolytic cleavage to form [(edta)RuV=O]-. Since [(edta)RuV=O]- was produced almost quantitatively in the reaction of 1 with the hydroperoxides tBuOOH and KHSO 5, the common mechanism is one of heterolytic scission of the O-O bond. The water soluble and easy to oxidize substrate 2,2′-azobis(3- ethylbenzithiazoline-6-sulfonate (ABTS), was employed to substantiate the mechanistic proposal. Reactions were carried out under pseudo-first order conditions for [ABTS] [hydroperoxide] ? [1], and were monitored as a function of time for the formation of the one-electron oxidation product ABTS+. The detailed suggested mechanism is consistent with the reported rate and activation parameters, and discussed in reference to the results reported for the reaction of [RuII(edta)(H 2O)]- with H2O2.

Evidence for urate hydroperoxide as an intermediate in the urate oxidase reaction [14]

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Hierarchically porous few-layer porphyrinic carbon nanosheets formed by a VO: X-templating method for high-efficiency oxygen electroreduction

A new vanadium oxide-templating synthesis strategy is used to synthesize porous few-layer porphyrinic carbon nanosheets (PPCNs) with highly efficient electrocatalytic activity for oxygen reduction reaction (ORR). Fe-porphyrin precursors were intercalated into V2O5 layers and directly transformed to carbon nanosheets after pyrolysis. Highly accessible porphyrinic Fe-N4 moieties embedded within few-layer carbon nanosheets with hierarchical porosity and high surface area (1600 m2 g-1) were obtained. The PPCNs were demonstrated as excellent non-precious metal catalysts for ORR in both alkaline and acidic media. Specifically, the PPCNs exhibited a more positive half-wave potential than commercial Pt/C (20 wt%) in an alkaline medium at a lower catalyst loading. Moreover through further pyrolysis treatment, the catalytic activity and durability of PPCNs for ORR in both media could be further improved. The novel synthesis method presented here opens up a new route to creating novel carbon nanomaterials for various applications.

Structural studies on manganese(III) and manganese(IV) complexes of tetrachlorocatechol and the catalytic reduction of dioxygen to hydrogen peroxide

The mononuclear complexes (Bu4N)[Mn(Cl4Cat) 2(H2O)(EtOH)] and (Bu4N)2[Mn(Cl 4Cat)3] (H2Cat=1,2-dihydroxybenzene) have been synthesised and characterised by X-ray diffraction. This work provides a direct, independent, synthesis of these complexes and an interesting example of how solvent effects can promote the formation of either a manganese(III) or manganese(IV) complex of the same ligand. The characterisation of (Bu 4N)[Mn(Cl4Cat)2(H2O)(EtOH)] supports previous work that manganese(III) is extremely reluctant to form tris (catecholato) complexes due to the short 'bite distance' of catecholate oxygen atoms (2.79 ?) which are unable to span the elongated coordination axes of the Jahn-Teller distorted Mn(III) ion and explains the 2:1 and 3:1 tetrachlorocatechol:manganese ratios in the Mn(III) and Mn(IV) complexes, respectively. Hydrogen peroxide production using dioxygen and hydroxylamine as substrates in acetonitrile/water mixtures, under ambient conditions, can be demonstrated with both complexes, suggesting that neither labile coordination sites nor the oxidation state of the manganese are important to the catalytic system. Turn over frequencies (TOF, moles of H2O2 per moles of manganese per hour) of ～10000 h-1 are obtained and this compares very favourably with the commercial production of hydrogen peroxide by the autoxidation of 2-ethylanthrahydroquinone (AO process).

Crystalline-Water/Coordination Induced Formation of 3D Highly Porous Heteroatom-Doped Ultrathin Carbon Nanosheet Networks for Oxygen Reduction Reaction

Development of highly efficient electrocatalysts with low cost for oxygen reduction reaction (ORR) is crucial for their application in fuel cells and metal-air batteries. In this work, we report a synthesis of 3D heteroatom-doped ultrathin carbon nanosheet networks directly starting from solid raw materials. This method represents an operationally simple, general, and sustainable strategy to various ultrathin carbon nanosheet networks. Evaporation of crystalline water and coordination interaction are proposed to be responsible for the formation of the 3D carbon nanosheet networks. The carbon nanosheet networks possess high surface area with micro- and macropores, large pore volume, ultrathin nanosheet structure, and effective N/S-co-doping. The as-prepared materials show outstanding electrocatalytic ORR performance with more positive onset potential and half-wave potential, good methanol tolerance, and excellent stability, compared with those of the porous carbons derived from the ZIF counterpart and commercial Pt/C. This work not only provides highly active ORR electrocatalysts via an operationally simple and green process and also demonstrates a general method to prepare 3D ultrathin carbon nanosheet networks without any additional template and solvent.

Changes induced by transition metal oxides in Pt nanoparticles unveil the effects of electronic properties on oxygen reduction activity

Although the relevance of electronic effects in the electrocatalysis of the oxygen reduction reaction has been recognized, the impossibility of separating the effects of composition and particle size for Pt-based materials has hindered establishing clear activity-property relationships. Herein, we report a systematic study based on induced changes via the interactions of pure Pt nanoparticles with transition metal oxide/carbon supports (Pt/MOx/C catalysts, MOx = CeO2, SnO2, TiO2, ZrO2 and WO3). A thorough analysis of aberration-corrected HR-STEM images demonstrated that Pt particles are similar in size and shape for all catalysts, while the direct probing of electronic properties by in situ X-ray absorption spectroscopy evidenced charge transfer between Pt and the supports. This approach allowed ascribing the changes in electrocatalytic activity for oxygen reduction solely to the variations in the electronic vacancy of the Pt 5d band resulting from the interactions between the metal nanoparticles and the supports containing different transition metal oxides. Oxygen reduction was studied in acid and in alkaline solutions, and linear correlations between the kinetic current densities and the Pt 5d band vacancy of pure Pt nanoparticles were found in both media. Possible first steps of the reduction of oxygen are discussed to explain the trends observed. The results, evidencing that enhanced ORR activity on Pt particles is promoted by a lower 5d band vacancy in acid solutions and by a higher one in alkaline medium, provide new insights on the fundamental aspects of oxygen reduction, and open up new possibilities to develop catalysts with enhanced activity for fuel cell cathodes by tuning their electronic properties.

Spinel CoMn2O4 nanoparticles supported on a nitrogen and phosphorus dual doped graphene aerogel as efficient electrocatalysts for the oxygen reduction reaction

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Room-Temperature Rate Constant for the HO2 + HO2 Reaction at Low Pressures

The rate constant, k1, for the self-reaction of HO2, HO2 + HO2 -> H2O2 + O2, was investigated in a discharge-flow system at room temperature and low pressures (1-7 torr) of He carrier gas by laser magnetic resonance detection of HO2, OH, and NO2.Three different chemical reactions, F + H2O2, Cl + H2O2, and CH2OH + O2, were used as sources of HO2.Absolute concentrations of HO2 were determined by converting HO2 to OH and NO2, by reaction with NO, and calibrating the system with known concentrations of OH or NO2.The average values for k1 in a phosphoric acid and halocarbon wax-coated flow tube were (1.90 +/- ? = 0.05)E-12 and (1.54 +/- ? = 0.07)E-12 cm3 molecule-1 s-1, respectively, at 295 +/- 2 K, where the errors represent one standard deviation of the mean.These results indicate some effect from reactor surface coating.The recommended rate constant from this study is k1 = (1.5 +/- 0.3)E-12 cm3 molecule-1 s-1, where the error is at the 95percent confidence level and includes an estimate of systematic errors.This result combined with other recent studies indicates that the reaction has both pressure-independent and pressure-dependent mechanisms.

Electrocatalytic reduction of dioxygen by Mn(iii): Meso -tetra(N -methylpyridinium-4-yl)porphyrin in universal buffer

The electrochemical characterization of manganese(iii) meso-tetra(N-methylpyridinium-4-yl)porphyrin pentachloride ([Mn(TMPyP)Cl][Cl]4) via cyclic voltammetry (CV) and UV-vis spectroelectrochemistry (UV-vis SEC) was performed across the entire p

Key Single-Atom Electrocatalysis in Metal—Organic Framework (MOF)-Derived Bifunctional Catalysts

Metal–organic framework (MOF)-derived materials have attracted increasing interest and show promising catalytic performances in many fields. Intensive efforts have been focused on the structure design and metal-site integration in MOF-derived catalysts. However, the key catalytic processes related with the metal sites in MOF-derived catalysts that dominate the electrocatalytic performance still remain obscure. Herein, we show a neglected but critical issue in the pyrolytic synthesis of MOF-derived catalysts: the coupled evolution of dual sites, that is, metallic sites and single-atom metal sites. The identification of active sites of single-atom sites from the visible particles has been elucidated through the combined X-ray spectroscopic, electron microscopic, and electrochemical studies. Interestingly, after a total removal of metallic cobalt sites, catalysts with purified single-atom metal sites show no faltering activity for either the oxygen reduction reaction (ORR) or hydrogen evolution reaction (HER), while significantly enhanced ORR selectivity is achieved; this reveals the dominant activity and selectivity contribution from single-atom electrocatalysis. The insight of the coupled evolution of dual sites and the as-demonstrated dual-site decoupling strategies open up a new routine for the design and synthesis of MOF-derived catalysts with the optimized single-atom electrocatalysis towards various electrochemical reactions.

Tris(2,2'-bipyridine)ruthenium(II)-photosensitized Reductions of Methyl Viologen and Molecular Oxygen in a Network of Water-swollen Cation-exchange Resin

The visible-light-induced reduction of methyl viologen was found to occur in water-swollen cation-exchange resin, which adsorbed both Ru(bpy)32+ and methyl viologen (RMCA resin) with the aid of triethanolamine (TEA) as a donor.With illumination, the generation of hydrogen peroxide procceds in an oxygenated TEA solution containing RMCA resin.Hydrogen peroxide is produced via the superoxide ion, which is itself formed by the reaction of methyl viologen radical in the resin with the oxygen molecule in the bulk of the solution.The Ru(bpy)32+-photosensitized reaction processes leading to the generation of methyl viologen radical and hydrogen peroxide in the heterogeneous systems are discussed on the basis of the results obtained.

Evidence for the role of colloidal palladium in the catalytic formation of H2O2 from H2 and O2

The direct production of H2O2 from H2 and O2 (O2/H2 = 2) at 25°C and 760 Torr occurs in an aqueous phase over colloidal palladium that may be introduced either via PdCl2 or via Pd supported on silica gel (Pd/SiO2). In the latter case, aqueous HCl facilitates the dissolution of the supported Pd. The presence of colloidal palladium was confirmed by electron microscopy. When the solution was either 0.1 M or 1.0 M in HCl, removal of the silica, along with any remaining supported Pd, did not affect the rate of H2O2 formation because the amount of active colloidal Pd remained unchanged. The specific activity of the supported Pd is only 3% of that for colloidal Pd, probably because of transport limitations within the pores of the silica.

Electrocatalytic dioxygen reduction on underpotentially deposited Pb on Au(111) studied by an active site blocking strategy

Electrochemical measurements and in situ scanning tunneling microscopy (STM) were carried out to establish a structure-reactivity correlation for peroxide or dioxygen reduction on underpotentially deposited (upd) Pb on Au(111) in 0.1 M HClO4. STM imaging revealed the presence of Pb islands with height of 0.25 ± 0.05 nm at the potential of highest catalytic activity toward the O2 and H2O2 reduction. The full Pb monolayer formed at - 0.03 v vs. NHE showed about half the activity of the Pb islands. Ethanethiol (EtSH) considerably, but not completely, inhibited H2O2 reduction activity of the Pb island structure. EtSH introduction resulted in the formation of a 0.13-nm-high terrace along the edges of the Pb islands, which was assigned to EtSH bound to the Au surface near the Pb islands with the alkyl chain oriented roughly perpendicular to the surface. These results showed that edge sites around the Pb island were the active site of catalysis, though the sites atop the Pb islands might also take part in catalytic O2 reduction by Pb upd on Au(111).

Photoassisted Construction of Holey Defective g-C3N4 Photocatalysts for Efficient Visible-Light-Driven H2O2 Production

Holey defective g-C3N4 photocatalysts, which are easily prepared via a novel photoassisted heating process, are reported. The photoassisted treatment not only helps to create abundant holes, endowing g-C3N4 with more exposed catalytic active sites and crossplane diffusion channels to shorten the diffusion distance of both reactants from the surface to bulk and charge carriers from the bulk to surface, but also introduces nitrogen vacancies in the tri-s-triazine repeating units of g-C3N4, inducing the narrowing of intrinsic bandgap and the formation of defect states within bandgap to extend the visible-light absorption range and suppress the radiative electron–hole recombination. As a result, the holey defective g-C3N4 photocatalysts show much higher photocatalytic activity for H2O2 production with optimized enhancement up to ten times higher than pristine bulk g-C3N4. The newly developed synthetic strategy adopted here enables the sufficient utilization of solar energy and shows rather promising for the modification of other materials for efficient energy-related applications.

The screening of metal ion inhibitors for glucose oxidase based on the peroxidase-like activity of nano-Fe3O4

In this study, a colorimetric method is proposed based on the peroxidase-like activity of Fe3O4 magnetic nanoparticles for screening metal ion inhibitors for glucose oxidase activity. First, the glucose oxidase was typically used as a specific enzyme to catalyze the oxidation of β-d-glucose resulting in the generation of hydrogen peroxide. Next, having an inherent peroxidase-like activity, Fe3O4 magnetic nanoparticles were adopted as the catalyst. Then, the generated H2O2 was capable of participating in the oxidation of 3,3′,5,5′-tetramethylbenzidine to yield a blue colored product. Based on the above results, an in vitro screen model of metal ion inhibitors of glucose oxidase was thus established. Metal ions including Ca2+, Pb2+, Mn2+, Ag+, Al3+, Cu2+, Mg2+ and Zn2+ have been tested. Herein, towards the glucose oxidase activity, Ca2+, Pb2+, Mg2+ and Mn2+ showed no effect while Al3+ and Zn2+ displayed a slight activation, while of Ag+ and Cu2+ expressed a strong inhibition. The further detection of Ag+ and Cu2+ manifested that their IC50 were 0.662 μmol L-1 and 12.619 μmol L-1, respectively. The entire detection process could be accomplished within 15 min. This assay is economical, time-saving and highly-effective with definitely significant reference for the screening of metal ions as glucose oxidase inhibitors.

Theoretical Modelling and Facile Synthesis of a Highly Active Boron-Doped Palladium Catalyst for the Oxygen Reduction Reaction

A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode-electrode reaction of fuel cells, is sought for higher fuel-cell performance. Our theoretical modelling reveals that B-doped Pd (Pd-B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O2dissociation, suggesting Pd-B should be highly active for ORR. In fact, Pd-B, facile synthesized by an electroless deposition process, exhibits 2.2times and 8.8times higher specific activity and 14times and 35times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti-bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity. Better with a B in its bonnet: Theoretical modelling shows that B doping negatively shifts the surface core level of Pd and lowers the barrier to O2dissociation for the oxygen reduction reaction (ORR). A B-doped Pd nanoparticle catalyst was then rationally designed, synthesized in a facile manner by electroless deposition, and shown to be a highly active ORR catalyst compared to commercial Pd and Pt catalysts.

Activation of O2 by Organosilicon Reagents Yields Quantitative Amounts of H2O2 or (Me3Si)2O2 for Efficient O-Transfer Reactions

Molecular oxygen is kinetically inert and rarely used as a primary oxidant for low temperature selective oxygenation reactions. Here, we show that O2 is converted into H2O2 in almost quantitative yields (98 %) at ambient temperature and atmospheric pressure in the presence of bis(trimethylsilyl)-1,4-cyclohexadiene 1. Similarly, the reaction of O2 with dihydro-bis(trimethylsilyl) viologen 2 and pyrazine 3 yields bis(trimethylsilyl) peroxide (BTSP) in excellent yields (up to 99 %) at low temperature. Both processes demonstrate that readily available organosilicon reagents enable chemistry typically observed with mono-oxygenase co-enzymes, such as FADH2 and FMNH2, in biological systems, or at higher pressure via the industrial anthraquinone process. This efficient synthesis of H2O2 and BTSP directly from O2 is particularly attractive for the preparation of the corresponding O-17 and O-18 labeled reagents without the need of large excess amounts of O2. These are showcased in O-atom transfer reactions to various organic or inorganic substrates, in a two-step one-pot process, making the rapid and on-demand synthesis of large libraries of O-labeled compounds readily possible.

Production of Hydrogen Peroxide from Dioxygen and Hydroxylamine or Hydrazine catalysed by Manganese Complexes

Manganese(II) catecholate complexes efficiently catalyse the production of H2O2 from dioxygen in the range pH 7.5-8.6 using hydroxylamine or hydrazine as substrates: concentrations of hydrogen peroxide >0.2 mol dm-3 and turnover numbers /II> > 104 can be obtained.The rate of production and yields are very sensitive to the electronic effect of the substituents on the catecholate ring with the best results being achieved using 4,5-dihydroxybenzene-1,3-disulfonate.Deuteriation studies (using ND2OD) indicated that the reduction of O2 occurs via an electron trans fer from the substrate and a mechanism is proposed whereby both O2 and thec substarte become bound to manganese and the electron transfer is mediated through the manganese catecholate complex.

Control of Electrons' Spin Eliminates Hydrogen Peroxide Formation during Water Splitting

The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition, hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed, while the overall current through the cell, correlating with the water splitting process, is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements, in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells.

Oxygen reduction on nanocrystalline ruthenia-local structure effects

Nanocrystalline ruthenium dioxide and doped ruthenia of the composition Ru1-xMxO2 (M = Co, Ni, Zn) with 0 ≤ x ≤ 0.2 were prepared by the spray-freezing freeze-drying technique. The oxygen reduction activity and selectivity of the prepared materials were evaluated in alkaline media using the RRDE methodology. All ruthenium based oxides show a strong preference for a 2-electron oxygen reduction pathway at low overpotentials. The catalysts' selectivity shifts towards the 4-electron reduction pathway at high overpotentials (i.e. at potentials below 0.4 V vs. RHE). This trend is particularly noticeable on non-doped and Zn-doped catalysts; the materials containing Ni and Co produce a significant fraction of hydrogen peroxide even at high overpotentials. The suppression of the 4-electron reduction pathway on Ni and Co-doped catalysts can be accounted for by the presence of the Ni and Co cations in the cus binding sites as shown by the DFT-based analyses on non-doped and doped catalysts. This journal is

Photochemistry of Solid Ozone

Samples of neat solid ozone and ozone trapped in excess ice have been subjected to laser photolysis at 308 nm.Cross sections for photoabsorption and photodestruction of the ozone are reported.The quantum yield decreases from 1.5 +/- 0.2 in pure ozone to 0.4 +/- 0.2 for ozone in excess ice.These yields are consistent with a reaction mechanism in which electronically excited O(1D) atoms are responsible for the photochemistry.In neat ozone, the atoms react with a neighboring ozone molecule to form two oxygen molecules.In water, O(1D) reacts to form hydrogen peroxide, HCOOH.Ground-state oxygen atoms produced in the initial photolysis of ozone most likely undergo recombination with O2 to regenerate O3.

Hydrogen Abstraction and One-Electron Oxidation in Nickel(II)-Iminodiacetate Complexes

Reactions of nickel(II) iminodiacetates with OH radicals in aqueous solutions were studied by means of steady-state and pulse radiolysis.Radiolytic degradation of the complexes led to the formation of glycine and carbonyl compounds with similar yields.The OH radical attacks the metal complexes at the ligand rather than at the metal center, the product being a metal-coordinated radical.This carbon-centered radical undergoes disproponation into products.It may be also oxidized by O2 and Fe(CN)63-.In the presence of N2O the radical initiates a chain reaction in the case of the 1:1 complex but not with the 1:2 complex or the free ligand.Unlike OH, Br2- attacks the metal center rather than the ligand and oxidizes it to the NiIII complexes.This reaction is followed by oxidation of the carboxyl group of the ligby the NiIII to result in decarboxylation and production of formaldehyde.

Direct fabrication of tri-metallic PtPdCu tripods with branched exteriors for the oxygen reduction reaction

Design of multi-metallic nanocrystals with branched structures is very important for catalytic applications. Herein, a one-step synthesis of unique tri-metallic PtPdCu tripods with branched exteriors (PtPdCu TPs) in an aqueous solution is presented. Benefiting from their spatially and locally separated branches and tri-metallic compositions, the PtPdCu TPs exhibit superior activity and durability for the oxygen reduction reaction. The newly designed PtPdCu TPs are quite different from previous tripods in their branched exteriors. The developed one-step method is very feasible for the preparation of Pt-based multi-metallic tripods with designed compositions and desired performances.

A sol-gel pretreatment combined strategy for constructing cobalt-embedded and nitrogen-doped carbon matrix with high-density active sites as bifunctional oxygen reduction and evolution electrocatalysts

Developing highly efficient bifunctional oxygen electrocatalysts via cost-effective methods is of great significance for energy storage and conversion systems but still full of challenges. In this work, a simple and eco-friendly method which involves a sol-gel pretreatment on multiple precursors and subsequent pyrolysis is designed to synthesize Co nanoparticles embedded and nitrogen-doped porous carbon (Co@NC). The sol-gel pretreatment ensures the high dispersion of all precursors, which is beneficial to the formation of uniform and highly dense active sites. After pyrolysis, acid treatment removes the unencapsulated Co nanoparticles on the surface to form porous structure and increase the mass activity. Benefiting from the synthetic strategy, the porous Co@NC-850 with large surface area, high density of active sites (graphitic N, pyridinic N and Co-Nx) exhibits comparable oxygen reduction performance (E1/2 = 0.85 V vs. reversible hydrogen electrode) to that of commercial Pt/C and better oxygen evolution activity (with an overpotential of 350 mV at 10 mA cm?2) with respect to RuO2. The potential gap ΔE (between the oxygen evolution potential at 10 mA cm?2 and oxygen reduction E1/2) for Co@NC-850 is only 0.73 V. Compared with the state-of-the-art bifunctional oxygen electrocatalysts, Co@NC-850 shows obvious advantages in bifunctional activity and durability. The results in the present work will shed light on the development of other carbonaceous materials as the bifunctional oxygen electrocatalysts for energy storage and electrochemical devices.

Biphenyl appended non-noble metal complexes as electrocatalysts for the electrochemical oxygen reduction reaction

The oxygen reduction reaction (ORR) is one of the most important reactions in many electrochemical processes. There has been a growing interest in the replacement of noble metal electrocatalysts for oxygen reduction reaction (ORR). In continuation of these efforts herein we report the design and synthesis of biphenyl appended non-noble transition metal and Zn(II) complexes as electrocatalysts in the aforementioned reaction. In this regard nitrogen-based bidentate ligand, 6-(quinolin-8-yl)-6,7-dihydro-5H-dibenzo[c,e]azepine as Ligand, L was synthesized and used for the preparation of a series of mononuclear Ni(II) and Zn(II) complexes, [ML(X)2] which differ only by the halide ion attached to the respective metal center. All complexes of this series showed tetrahedral geometry regardless of the halide ion and metal center (Ni/Zn). The complexes were characterized by different spectroscopic techniques. The triflate (OTf) complexes of Fe(II) and Cu(II) were also synthesized to evaluate their ORR activity. All the complexes were investigated for their electrocatalytic activity in oxygen reduction reaction (ORR) in which complex 1, [NiL(Cl)2] showed the highest activity with an onset potential of 0.75 V. The remaining complexes also showed significant ORR performance with onset potentials close to that of complex 1.

An Iron(III) Superoxide Corrole from Iron(II) and Dioxygen

A new structurally characterized ferrous corrole [FeII(ttppc)]? (1) binds one equivalent of dioxygen to form [FeIII(O2?.)(ttppc)]? (2). This complex exhibits a 16/18O2-isotope sensitive ν(O-O) stretch at 1128 cm?1 concomitantly with a single ν(Fe-O2) at 555 cm?1, indicating it is an η1-superoxo (“end-on”) iron(III) complex. Complex 2 is the first well characterized Fe-O2 corrole, and mediates the following biologically relevant oxidation reactions: dioxygenation of an indole derivative, and H-atom abstraction from an activated O?H bond.

Bimetallic zeolite-imidazole framework-based heterostructure with enhanced photocatalytic hydrogen production activity

Bimetallic zeolite-imidazole frameworks with controllable flat band position, band gap and hydrogen evolution reaction characteristics were adopted as a photocatalytic hydrogen production catalyst. Furthermore, the g-C3N4-MoS22D-2D surface heterostructure was introduced to the ZnM-ZIF to facilitate the separation as well as utilization efficiency of the photo-exited charge carriers in the ZnM-ZIFs. On the other hand, the ZnM-ZIFs not only inhibited the aggregation of the g-C3N4-MoS2heterostructure, but also improved the separation and transport efficiency of charge carriers in g-C3N4-MoS2. Consequently, the optimal g-C3N4-MoS2-ZnNi-ZIF exhibited an extraordinary photocatalytic hydrogen evolution activity 214.4, 37.5, and 3.7 times larger than that of the pristine g-C3N4, g-C3N4-ZnNi-ZIF and g-C3N4-MoS2, respectively, and exhibited a H2-evolution performance of 77.8 μmol h?1g?1under UV-Vis light irradiation coupled with oxidation of H2O into H2O2. This work will furnish a new MOF candidate for photocatalysis and provide insight into better utilization of porous MOF-based heterostructures for hydrogen production from pure water.