16873-17-9

Upstream product

• 7732-18-5 water 
• 558-20-3 methane 
• 7789-20-0 water-d2 
• 7440-23-5 sodium 
• 13537-07-0 silane-d4 
• 7440-21-3 monosilane 
• 17030-72-7 trideuteriomethylium 
• 60094-88-4 CH₂⁽²⁾H⁽¹⁺⁾ 
• 58576-33-3 CH⁽²⁾H₂⁽¹⁺⁾ 
• 1076-43-3 benzene-d6 
• 1333-74-0 hydrogen 
• 13762-18-0 half-deuterated hydrogen sulphide 
• 7783-06-4 hydrogen sulfide 
• 13536-94-2 deuterium sulfide 

Downstream Products

• 7789-20-0 water-d2 
• 14940-63-7 water 
• 1333-74-0 hydrogen 
• 7698-05-7 hydrogen chloride 
• 872215-16-2 Zr(OH)(O⁽²⁾H) 
• 872207-78-8 Zr(OH)2(⁽¹⁸⁾OH)2 
• 872207-76-6 Zr(O⁽²⁾H)4 
• 756456-88-9 zirconium tetrahydroxide 
• 16873-17-9 deuterium D2, ortho 
• 13780-28-4 ammonia-d2 
• 13550-49-7 ammonia-d3 
• 15123-00-9 ammonia 
• 7783-06-4 hydrogen sulfide 
• 13762-18-0 half-deuterated hydrogen sulphide 

Relevant academic research and scientific papers

Introducing Water-Network-Assisted Proton Transfer for Boosted Electrocatalytic Hydrogen Evolution with Cobalt Corrole

Proton transfer is vital for many biological and chemical reactions. Hydrogen-bonded water-containing networks are often found in enzymes to assist proton transfer, but similar strategy has been rarely presented by synthetic catalysts. We herein report the Co corrole 1 with an appended crown ether unit and its boosted activity for the hydrogen evolution reaction (HER). Crystallographic and 1H NMR studies proved that the crown ether of 1 can grab water via hydrogen bonds. By using protic acids as proton sources, the HER activity of 1 was largely boosted with added water, while the activity of crown-ether-free analogues showed very small enhancement. Inhibition studies by adding 1) external 18-crown-6-ether to extract water molecules and 2) potassium ion or N-benzyl-n-butylamine to block the crown ether of 1 further confirmed its critical role in assisting proton transfer via grabbed water molecules. This work presents a synthetic example to boost HER through water-containing networks.

Pd/C-Catalyzed H2 Evolution from Tetrahydroxydiboron Hydrolysis

The production of H2 from non-fossil sources is a key research challenge to contributing solving the forthcoming energy problem. Aqueous solutions of tetrahydroxydiboron have very recently appeared as a H2 source, from which both hydrogen atoms are provided by water, in the presence of highly sophisticated nanocatalysts. Herein, commercial and cheap Pd/C is shown to be an efficient and recyclable catalyst for H2 evolution upon tetrahydroxydiboron hydrolysis. Graphic Abstract: [Figure not available: see fulltext.]

Bis-Imidazole Methane Ligated Ruthenium(II) Complexes: Synthesis, Characterization, and Catalytic Activity for Hydrogen Production from Formic Acid in Water

A series of half sandwich arene-ruthenium complexes [(η6-arene)RuCl(κ2-L)]+ ([Ru]-1-[Ru]-10) containing bis-imidazole methane-based ligands {4,4′-(phenylmethylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L1), {4,4′-((4-methoxyphenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L2), {4,4′-((2-methoxyphenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L3), {4,4′-((4-chlorophenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L4), and {4,4′-((2-chlorophenyl)methylene)bis(2-ethyl-5-methyl-1H-imidazole)} (L5) are synthesized. The synthesized and purified complexes ([Ru]-1-[Ru]-10) are further employed for hydrogen production from formic acid in aqueous medium. Among the investigated complexes, [(η6-p-cymene)RuCl(κ2-L2)]+ [Ru]-2, having Ru(II) coordinated 4-methoxy phenyl substituted bis-imidazole methane ligand (L2), outperformed over others, displaying a higher catalytic turnover of 8830 and high efficiency (TOF = 1545 h-1) with appreciably high long-term stability for formic acid dehydrogenation in water.

Activation of Molecular Hydrogen by Inter- and Intramolecular Al?N Lewis Pairs

The field of frustrated Lewis pair chemistry offers many opportunities to activate molecular hydrogen, but Al?N systems have not been established yet. In this work, we describe several intermolecular classical Al?N Lewis pairs and an intramolecular ortho-

Hydrolysis of B2pin2 over Pd/C Catalyst: High Efficiency, Mechanism, and in situ Tandem Reaction

A facile and effective synthesis of H2 or D2 from Pd/C catalyzed hydrolysis of B2pin2 has first been developed. Among them, B2pin2 is frequently used for borylation reaction, and has rarely been used for hydrogen evolution. The kinetic isotope effects (KIEs) and tandem reaction for diphenylacetylene and norbornene hydrogenation have confirmed both two H atoms of H2 gas are provided from H2O. This is contrary to other boron compounds hydrolysis (including NH3BH3, NaBH4), which generates H2 with only one H atom provided by water and the other one by boron compounds. Note that the hydrolysis of B2pin2 in D2O also provides an easy and useful synthesis of D2.

Acid- and Base-Catalyzed Hydrolytic Hydrogen Evolution from Diboronic Acid

The efficient production of H2 from hydrogen-rich sources, particularly from water, is a crucial task and a great challenge, both as a sustainable energy source and on the laboratory scale for hydrogenation reactions. Herein, a facile and effective synthesis of H2 and D2 from only acid- or base-catalyzed metal-free hydrolysis of B2(OH)4, a current borylation reagent, has been developed without any transition metal or ligand. Acid-catalyzed H2 evolution was completed in 4 min, whereas the base-catalyzed process needed 6 min. The large kinetic isotopic effects for this reaction with D2O, deuteration experiments and mechanistic studies have confirmed that both H atoms of H2 originate from water using either of these reactions. This new, metal-free catalytic system holds several advantages, such as high efficiency, simplicity of operation, sustainability, economy, and potential further use.

Bifunctional activation of amine-boranes by the W/Pd bimetallic analogs of “frustrated Lewis pairs”

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH2P(t-C4H9)2)2C6H4) and acidic [LWH(CO)3] (L = Cp (1a), Tp (1b); Cp = η5-cyclopentadienyl, Tp = κ3-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)2(μ-CO)?Pd(PCP)] (4a,4b), which catalyze amine-borane (Me2NHBH3tBuNH2BH3) dehydrogenation. The combination of variable-temperature (1H,31P{1H},11B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η1-borane complex [(PCP)Pd(Me2NHBH3)]+[LW(CO3)]?(5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species4are easily regenerated through hydrogen evolution in the reaction between two hydrides.

Ammonia-Borane Dehydrogenation Catalyzed by Dual-Mode Proton-Responsive Ir-CNNHComplexes

Metal complexes incorporating proton-responsive ligands have been proved to be superior catalysts in reactions involving the H2 molecule. In this contribution, a series of IrIII complexes based on lutidine-derived CNNH pincers containing N-heterocyclic carbene and secondary amino NHR [R = Ph (4a), tBu (4b), benzyl (4c)] donors as flanking groups have been synthesized and tested in the dehydrogenation of ammonia-borane (NH3BH3, AB) in the presence of substoichiometric amounts (2.5 equiv) of tBuOK. These preactivated derivatives are efficient catalysts in AB dehydrogenation in THF at room temperature, albeit significantly different reaction rates were observed. Thus, by using 0.4 mol% of 4a, 1.0 equiv of H2 per mole of AB was released in 8.5 min (turnover frequency (TOF50%) = 1875 h-1), while complexes 4b and 4c (0.8 mol%) exhibited lower catalytic activities (TOF50% = 55-60 h-1). 4a is currently the best performing IrIII homogeneous catalyst for AB dehydrogenation. Kinetic rate measurements show a zero-order dependence with respect to AB, and first order with the catalyst in the dehydrogenation with 4a (-d[AB]/dt = k[4a]). Conversely, the reaction with 4b is second order in AB and first order in the catalyst (-d[AB]/dt = k[4b][AB]2). Moreover, the reactions of the derivatives 4a and 4b with an excess of tBuOK (2.5 equiv) have been analyzed through NMR spectroscopy. For the former precursor, formation of the iridate 5 was observed as a result of a double deprotonation at the amine and the NHC pincer arm. In marked contrast, in the case of 4b, a monodeprotonated (at the pincer NHC-arm) species 6 is observed upon reaction with tBuOK. Complex 6 is capable of activating H2 reversibly to yield the trihydride derivative 7. Finally, DFT calculations of the first AB dehydrogenation step catalyzed by 5 has been performed at the DFT//MN15 level of theory in order to get information on the predominant metal-ligand cooperation mode.

Photocatalytic proton reduction by a computationally identified, molecular hydrogen-bonded framework

We show that a hydrogen-bonded framework, TBAP-α, with extended π-stacked pyrene columns has a sacrificial photocatalytic hydrogen production rate of up to 3108 μmol g-1 h-1. This is the highest activity reported for a molecular organic crystal. By comparison, a chemically-identical but amorphous sample of TBAP was 20-200 times less active, depending on the reaction conditions, showing unambiguously that crystal packing in molecular crystals can dictate photocatalytic activity. Crystal structure prediction (CSP) was used to predict the solid-state structure of TBAP and other functionalised, conformationally-flexible pyrene derivatives. Specifically, we show that energy-structure-function (ESF) maps can be used to identify molecules such as TBAP that are likely to form extended π-stacked columns in the solid state. This opens up a methodology for the a priori computational design of molecular organic photocatalysts and other energy-relevant materials, such as organic electronics.

Photocatalyst Z-scheme system composed of a linear conjugated polymer and BiVO4for overall water splitting under visible light

Linear conjugated polymers have potential as photocatalysts for hydrogen production from water but so far, most studies have involved non-scalable sacrificial reagents. Z-schemes comprising more than one semiconductor are a potential solution, but it is challenging to design these systems because multiple components must work together synergistically. Here, we show that a conjugated polymer photocatalyst for proton reduction can be coupled in a Z-scheme with an inorganic water oxidation photocatalyst to promote overall water splitting without any sacrificial reagents. First, a promising combination of an organic catalyst, an inorganic catalyst, and a redox mediator was identified by using high-throughput screening of a library of components. A Z-scheme system composed of P10 (homopolymer of dibenzo[b,d]thiophene sulfone)-Fe2+/Fe3+-BiVO4 was then constructed for overall water splitting under visible light irradiation. Transient absorption spectroscopy was used to assign timescales to the various steps in the photocatalytic process. While the overall solar-to-hydrogen efficiency of this first example is low, it provides proof of concept for other hybrid organic-inorganic Z-scheme architectures in the future. This journal is