64-17-5

An efficient Ni-Mo-K sulfide catalyst doped with CNTs for conversion of syngas to ethanol and higher alcohols

Wang, Ji-Jie,Xie, Jian-Rong,Huang, Yan-Hui,Chen, Bing-Hui,Lin, Guo-Dong,Zhang, Hong-Bin

, p. 44 - 51 (2013)

A type of Ni-Mo-K sulfide catalyst doped with CNTs for conversion of syngas to ethanol and higher alcohols was developed, and displayed high activity and selectivity for direct synthesis of C1-4-alcohols, especially ethanol, from syngas. Over a Ni0.5Mo1K0.5- 15%CNTs catalyst under the reaction conditions of 8.0 MPa and 593 K, the S(total oxy.) reached 64.1% (CO2-free), with the corresponding STY(total oxy.) being 113 mg h-1 g-1. Ethanol was the dominant product, with S(EtOH) and STY(EtOH) reaching 33.1% (CO2-free) and 55.6 mg h-1 g-1, respectively. This STY(EtOH)-value was 1.47 times that (37.9 mg h-1 g-1) of the CNTs-free counterpart under the same reaction conditions. Addition of a minor amount of CNTs to the sulfurized Ni0.5Mo1K0.5 catalyst caused little change in the Ea for the hydrogenation-conversion of syngas. Appropriately reducing CNT's grain-size could improve its capability to adsorb hydrogen, thus increasing CO hydrogenation-conversion, yet did not influence selectivity of the products. The present work demonstrated that CNTs as promoter function through their adsorbing/activating H2 to generate a surface micro-environment with higher stationary-state concentration of H-adspecies on the functioning catalyst. This resulted in a dramatic increase, at the surface of the functioning catalyst, of the molar percentage of catalytically active Mo4+/Mo5+ species in the total amounts of surface Mo. On the other hand, those active H-species adsorbed at the CNTs surface could be readily transferred to NiiMojK k active sites via the CNT-assisted hydrogen spillover. The aforementioned two factors both were conducive to increasing the rate of hydrogenation conversion of syngas.

Production of bio-ethanol by consecutive hydrogenolysis of corn-stalk cellulose

Chu, Dawang,Xin, Yingying,Zhao, Chen

, p. 844 - 854 (2021)

Current bio-ethanol production entails the enzymatic depolymerization of cellulose, but this process shows low efficiency and poor economy. In this work, we developed a consecutive aqueous hydrogenolysis process for the conversion of corn-stalk cellulose to produce a relatively high concentration of bio-ethanol (6.1 wt%) without humin formation. A high yield of cellulose (ca. 50 wt%) is extracted from corn stalk using a green solvent (80 wt% 1,4-butanediol) without destroying the structure of the lignin. The first hydrothermal hydrogenolysis step uses a Ni–WOx/SiO2 catalyst to convert the high cumulative concentration of cellulose (30 wt%) into a polyol mixture with a 56.5 C% yield of ethylene glycol (EG). The original polyol mixture is then subjected to subsequent selective aqueous-phase hydrogenolysis of the C–O bond to produce bioethanol (75% conversion, 84 C% selectivity) over the modified hydrothermally stable Cu catalysts. The added Ni component favors the good dispersion of Cu nanoparticles, and the incorporated Au3+ helps to stabilize the active Cu0-Cu+ species. This multi-functional catalytic process provides an economically competitive route for the production of cellulosic ethanol from raw lignocellulose.

Laser-Microstructured Copper Reveals Selectivity Patterns in the Electrocatalytic Reduction of CO2

Ackerl, Norbert,Martín, Antonio J.,Pérez-Ramírez, Javier,Veenstra, Florentine L. P.

, p. 1707 - 1722 (2020)

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Photochemical Preparation of Anatase Titania Supported Gold Catalyst for Ethanol Synthesis from CO2 Hydrogenation

Wang, Dong,Bi, Qingyuan,Yin, Guoheng,Wang, Peng,Huang, Fuqiang,Xie, Xiaoming,Jiang, Mianheng

, p. 11 - 22 (2018)

Abstract: Hydrogenation of the greenhouse gas CO2 to higher alcohols through catalysis holds great promise for resource transformation in low-carbon energy supply system, but the efficient and selective synthesis of value-added ethanol by a robust heterogeneous catalyst under relatively mild conditions remains a major challenge. Based on our previous work on Au/TiO2 as an active and selective catalyst for ethanol synthesis, we report here that a facile photochemical route can be used for the preparation of anatase TiO2 supported gold catalyst (Au/a-TiO2) for efficient hydrogenation of CO2. Compared with the conventional deposition-precipitation method requiring strong br?nsted base and flammable H2 gas in the complicated and time-consuming process, the photochemical way for the facile preparation of supported gold catalyst shows the advantages of green and energy-saving. Of significant importance is that an impressive space-time-yield of 869.3?mmol?gAu?1?h?1, high selectivity, and excellent stability can be readily attained at 200?°C and total pressure of 6?MPa. The effects of irradiation time, solvent, and metal loading or Au particle size on ethanol synthesis are systematically investigated. Graphical Abstract: [Figure not available: see fulltext.].

Fe/Fe3C Boosts H2O2 Utilization for Methane Conversion Overwhelming O2 Generation

Xing, Yicheng,Yao, Zheng,Li, Wenyuan,Wu, Wenting,Lu, Xiaoqing,Tian, Jun,Li, Zhongtao,Hu, Han,Wu, Mingbo

, p. 8889 - 8895 (2021)

H2O2 as a well-known efficient oxidant is widely used in the chemical industry mainly because of its homolytic cleavage into .OH (stronger oxidant), but this reaction always competes with O2 generation resulting in H2O2 waste. Here, we fabricate heterogeneous Fenton-type Fe-based catalysts containing Fe-Nx sites and Fe/Fe3C nanoparticles as a model to study this competition. Fe-Nx in the low spin state provides the active site for .OH generation. Fe/Fe3C, in particular Fe3C, promotes Fe-Nx sites for the homolytic cleavages of H2O2 into .OH, but Fe/Fe3C nanoparticles (Fe0 as the main component) with more electrons are prone to the undesired O2 generation. With a catalyst benefiting from finely tuned active sites, 18 % conversion rate for the selective oxidation of methane was achieved with about 96 % selectivity for liquid oxygenates (formic acid selectivity over 90 %). Importantly, O2 generation was suppressed 68 %. This work provides guidance for the efficient utilization of H2O2 in the chemical industry.

Kinetics of hydrogenation of acetic acid to ethanol

Chen, Qiang,Zhang, Xuebing,Tian, Shuxun,Long, Junying,Meng, Xiangkun,Sun, Qi,Li, Yonglong

, p. 2915 - 2923 (2019)

The intrinsic kinetic behaviour of catalytic hydrogenation of acetic acid in vapour phase was studied over a multi-metallic catalyst. The rate expression was derived from the sequence of elementary reaction steps based on a Langmuir-Hinshelwood-model involving two types of active sites. Experiments were carried out in a fixed bed reactor, which is similar to an isothermal integral reactor designed to excluding the negative effects of internal and external diffusion. The reaction conditions investigated were as follow:reaction temperature 275-325 oC, reaction pressure1.5-3.0 MPa, liquid hourly space velocity (sv) 0.3-1.2 h-1, molar ratio of hydrogen to acetic acid (H/AC) 8:20. The results show that conversion of acetic acid increases with increasing the reaction temperature and pressure, but decreases with increasing the space velocity and H/AC. Furthermore, reducing the reaction pressure and increasing reaction temperature, space velocity and H/AC can improve the reaction selectivity of acetic acid to ethanol. The established kinetic model results agreed with experimental results. The relative difference between the calculated value and the experimental value is less than 6 %. The values of model parameters are consistent with the three thermodynamic constraints. The study provided evidence that the intrinsic kinetic model is suitable both mathematically and thermodynamically, and it could be useful in guiding reactor design and optimization of operating conditions.

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Jatkar,Gajendragad

, p. 798 (1937)

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Porous Copper Microspheres for Selective Production of Multicarbon Fuels via CO2 Electroreduction

Zou, Chengqin,Xi, Cong,Wu, Deyao,Mao, Jing,Liu, Min,Liu, Hui,Dong, Cunku,Du, Xi-Wen

, (2019)

The electroreduction of carbon dioxide (CO2) toward high-value fuels can reduce the carbon footprint and store intermittent renewable energy. The iodide-ion-assisted synthesis of porous copper (P-Cu) microspheres with a moderate coordination number of 7.7, which is beneficial for the selective electroreduction of CO2 into multicarbon (C2+) chemicals is reported. P-Cu delivers a C2+ Faradaic efficiency of 78 ± 1% at a potential of ?1.1 V versus a reversible hydrogen electrode, which is 32% higher than that of the compact Cu counterpart and approaches the record (79%) reported in the same cell configuration. In addition, P-Cu shows good stability without performance loss throughout a continuous operation of 10 h.

Encapsulation of Two Potassium Cations in Preyssler-Type Phosphotungstates: Preparation, Structural Characterization, Thermal Stability, Activity as an Acid Catalyst, and HAADF-STEM Images

Hayashi, Akio,Ota, Hiromi,López, Xavier,Hiyoshi, Norihito,Tsunoji, Nao,Sano, Tsuneji,Sadakane, Masahiro

, p. 11583 - 11592 (2016)

Dipotassium cation (K+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110K2]13-, was prepared by heating monobismuth (Bi3+)-encapsulated Preyssler-type phosphotungstate, [P5W30O110Bi(H2O)]12-, in acetate buffer in the presence of an excess amount of potassium cations. Characterization of the isolated potassium salt, K13[P5W30O110K2] (1a), and its acid form, H13[P5W30O110K2] (1b), by single crystal X-ray structure analysis, 31P and 183W nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy, cyclic voltammetry (CV), high-resolution electrospray ionization mass spectroscopy (HR-ESI-MS), and elemental analysis revealed that two potassium cations are encapsulated in the Preyssler-type phosphotungstate molecule with formal D5h symmetry, which is the first example of a Preyssler-type compound with two encapsulated cations. Incorporation of two potassium cations enhances the thermal stability of the potassium salt, and the acid form shows catalytic activity for hydration of ethyl acetate. Packing of the Preyssler-type molecules was observed by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM).

Anderson et al.

, p. 2418,2422 (1952)

Hydrolysis of S-2-aminoethylcysteinyl peptide bond by Achromobacter protease I.

Masaki,Takiya,Tsunasawa,Kuwahara,Sakiyama,Soejima

, p. 215 - 216 (1994)

The substrate specificity of Achromobacter protease I (API) was examined for S-2-aminoethyl(AE)cysteinyl bonds in Bz-AEC-OMe/OEt, Bz-AEC-NH2, and AE-insulin B chain. The protease hydrolyzed all of the tested AE-cysteinyl bonds at the same rate as that of lysyl bonds. Kinetic parameters were estimated for this hydrolysis reaction.

CO2 Hydrogenation to Ethanol over Cu@Na-Beta

Ding, Liping,Shi, Taotao,Gu, Jing,Cui, Yun,Zhang, Zhiyang,Yang, Changju,Chen, Teng,Lin, Ming,Wang, Peng,Xue, Nianhua,Peng, Luming,Guo, Xuefeng,Zhu, Yan,Chen, Zhaoxu,Ding, Weiping

, p. 2673 - 2689 (2020)

Here, we report a high-performance catalyst Cu@Na-Beta, prepared via a unique method to embed 2～5 nm Cu nanoparticles in crystalline particles of Na-Beta zeolite, for CO2 hydrogenation to ethanol as the only organic product in a traditional fixed-bed reactor. The ethanol yield in a single pass can reach ～14% at 300°C, ～12,000 mL·gcat?1·h?1, and 2.1 MPa, corresponding to a space-time yield of ～398 mg·gcat?1·h?1. The key step of the reaction is considered as the rapid bonding of CO2? with surface methyl species at step sites of Cu nanoparticles to CH3COO? that converts to ethanol in following hydrogenation steps. The points of the catalyst seemed to be that the irregular copper nanoparticles stuck in zeolitic frameworks offer high density of step sites and the intimate surrounding of zeolitic frameworks strongly constrain the CO2 reactions at the copper surface and block by-products, such as methanol, formic acid, and acetyl acid. The high-performance catalyst Cu@Na-Beta, prepared via a unique method to embed 2～5 nm Cu nanoparticles in crystalline particles of Na-Beta zeolite, is reported for CO2 hydrogenation to ethanol as the only organic product in a traditional fixed-bed reactor. The ethanol yield in a single pass can reach ～14% at 300°C, ～12,000 mL·gcat?1·h?1, and 2.1 MPa, corresponding to space-time yield of ～398 mg·gcat?1·h?1. The key step of the reaction is the rapid bonding of CO2? with surface methyl species at step sites of Cu nanoparticles to CH3COO?, which converts to ethanol in the following hydrogenation steps. The points of the catalyst seem to be that the irregular copper nanoparticles stuck in zeolitic frameworks offer a high density of step sites and that the intimate surrounding of zeolitic frameworks strongly constrains the CO2 reactions at the copper surface and blocks byproducts such as methanol, formic acid, and acetyl acid. CO2 direct reduction to ethanol is a much-anticipated research topic worldwide. A big progress has been made in the current investigation toward industry application. A high-performance catalyst Cu@Na-Beta, prepared via a unique method to embed 2～5 nm Cu nanoparticles in crystalline particles of Na-Beta zeolite, is reported for CO2 hydrogenation to ethanol in a traditional fixed-bed reactor, with ethanol space-time yield of ～398 mg·gcat?1·h?1. Peripherals-surrounded catalysts, which may be called mesocatalysts, appear to be one focus of future investigations on catalysis.

Active sites in CO2 hydrogenation over confined VOx-Rh catalysts

Wang, Guishuo,Luo, Ran,Yang, Chengsheng,Song, Jimin,Xiong, Chuanye,Tian, Hao,Zhao, Zhi-Jian,Mu, Rentao,Gong, Jinlong

, p. 1710 - 1719 (2019)

Metal oxide-promoted Rh-based catalysts have been widely used for CO2 hydrogenation, especially for the ethanol synthesis. However, this reaction usually suffers low CO2 conversion and alcohols selectivity due to the formation of byp

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Roberts,Yancey

, p. 5943 (1952)

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Reduction of Potassium Acetate and Potassium Propionate With Lithium Aluminium Hydride in the Presence of Phase-Transfer Catalysts

Szakacs, Sandor,Goeboeloes, Sandor,Szammer, Janos

, p. 883 - 886 (1981)

Ethyl alcohol and propyl alcohol can be prepared with good yields from potassium carboxylates by the reduction with lithium aluminium hydride in the presence of different phase transfer catalysts. - Keywords: Crown ethers; Phase-transfer catalysts; Reduction

Effect of the ZnO/SiO2ratio on the structure and catalytic activity of Cu/SiO2and Cu/ZnO catalysts in water-containing ester hydrogenation

Chen, Zheng,Wei, Shuwei,Zhao, Xueying,Wang, Dengfeng,Chen, Jiangang

, p. 14560 - 14567 (2020)

The effects of the ZnO/SiO2 ratio on the water tolerance of Cu/SiO2 and Cu/ZnO catalysts were studied by ethyl acetate with 5 wt% water hydrogenation. Notably, the addition of an appropriate amount of ZnO endows Cu/SiO2 catalysts with satisfactory water-tolerant hydrogenation performance by a decrease in the reaction temperature without sacrificing conversion. At the same time, agglomeration can be alleviated for Cu/ZnO catalysts due to the optimal addition of SiO2, which is considered as a partition material that effectively hinders the agglomeration of the Cu/ZnO catalyst. However, the addition of ZnO was not favourable for the copper dispersion of Cu/SiO2. The stability of Cu/SiO2 catalyst quickly degraded due to excessive ZnO being introduced by sintering. The copper dispersion of Cu/ZnO catalysts initially increased with increasing SiO2 content, but then decreased. The addition of excess SiO2 also led to decreased activity and rapid deactivation of the Cu/ZnO catalyst. In our study, the appropriate addition of ZnO (5 wt%) and SiO2 (5 wt%) had a positive effect on the Cu/SiO2 and Cu/ZnO catalysts, respectively.

Near-infrared kinetic spectroscopy of the HO2and C 2H5O2 self-reactions and cross reactions

Noell,Alconcel,Robichaud,Okumura,Sander

, p. 6983 - 6995 (2010)

The self-reactions and cross reactions of the peroxy radicals C 2H5O2 and HO2 were monitored using simultaneous independent; spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO 2, and UV absorption monitored C2H2O 2. The temperature dependences of these reactions were investigated over a range of interest; to tropospheric chemistry, 221-296 K. The Arrhenius expression determined for the cross reaction, k2(T) = (6.01 +1.95 -1.47) x 10-13 exp((638 ± 73)/T) cm3 molecules-1 s-1 is in agreement with other work from the literature. The measurements of the HO2 self-reaction agreed with previous work from, this lab and were not further refined. The C2H5O2 self-reaction is complicated by secondary production of HO2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part; by measurement of the secondary HO2. The Arrhenius expression for the self-reaction rate constant is k3(T) = (1.29 +0.34 -0.27) x 10-13 exp((-23 ± 61)/T) cm3 molecules-1 s- and the branching fraction value is α = 0.28 ± 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the blanching fraction. The results suggest that better characterization of the products from RO2 self-reactions are required.

Photoinduction of Cu single atoms decorated on UiO-66-NH2for enhanced photocatalytic reduction of CO2to liquid fuels

Wang, Gang,He, Chun-Ting,Huang, Rong,Mao, Junjie,Wang, Dingsheng,Li, Yadong

, p. 19339 - 19345 (2020)

Photocatalytic reduction of CO2 to value-added fuels is a promising route to reduce global warming and enhance energy supply. However, poor selectivity and low efficiency of catalysts are usually the limiting factor of their applicability. Herein, a photoinduction method was developed to achieve the formation of Cu single atoms on a UiO-66-NH2 support (Cu SAs/UiO-66-NH2) that could significantly boost the photoreduction of CO2 to liquid fuels. Notably, the developed Cu SAs/UiO-66-NH2 achieved the solar-driven conversion of CO2 to methanol and ethanol with an evolution rate of 5.33 and 4.22 μmol h-1 g-1, respectively. These yields were much higher than those of pristine UiO-66-NH2 and Cu nanoparticles/UiO-66-NH2 composites. Theoretical calculations revealed that the introduction of the Cu SAs on the UiO-66-NH2 greatly facilitates the conversion of CO2 to CHO? and CO? intermediates, leading to excellent selectivity toward methanol and ethanol. This study provides new insights for designing high-performance catalyst for photocatalytic reduction of CO2 at the atomic scale.

Cu9-Alx-Mgy catalysts for hydrogenation of ethyl acetate to ethanol

Tian, Jingxia,Hu, Jun,Shan, Wenjuan,Wu, Peng,Li, Xiaohong

, p. 108 - 115 (2017)

Cu9-Alx or Cu9-Alx-My (M?=?Mg, Ca, Ba or Sr) catalysts were prepared by a deposition-precipitation method, characterized by means of H2-TPR, XRD and N2 sorption, and applied for hydrogenation of ethyl acetate to ethanol in a fixed-bed reactor. The molar ratio of Cu/Al or Cu/Al/M and the reaction parameters were investigated thoroughly. As a result, the Cu9-Al0.5-Mg1.5 catalyst with higher specific surface area, lower initial reduction temperature and better metal dispersion furnished 97.8% ethyl acetate conversion with 98% selectivity to ethanol under optimal reaction conditions. Moreover, the Cu9-Al0.5-Mg1.5 catalyst also showed good lifetime and neither the activity nor selectivity decreased during 210?h test. Based on the characterization of the Cu9-Al0.5-Mg1.5 catalyst, the optimal Cu+/Cu0 proportion played a key role in determining the superior performance.

Insight into the Correlation between Cu Species Evolution and Ethanol Selectivity in the Direct Ethanol Synthesis from CO Hydrogenation

Li, Xiao-Li,Yang, Guo-Hui,Zhang, Meng,Gao, Xiao-Feng,Xie, Hong-Juan,Bai, Yun-Xing,Wu, Ying-Quan,Pan, Jun-Xuan,Tan, Yi-Sheng

, p. 1123 - 1130 (2019)

Cu/SiO2 catalyst was prepared by the ammonia evaporation method for the direct synthesis of ethanol from CO hydrogenation. The catalyst exhibited the initial ethanol selectivity as high as 40.0 wt %, which dramatically decreased from 40.0 to 9.6 wt % on the stream of 50 h. XRD, XPS, TEM and N2O titration techniques were employed to elucidate the ethanol selectivity change and catalyst structure evolution during reaction process. The experiment and characterization results indicated that both Cu+/(Cu++Cu0) value and copper crystallite size had great effects on the ethanol selectivity. During the initial 38 h, the ethanol selectivity obviously decreased from 40.0 to 18.2 wt %, and Cu+/(Cu++Cu0) value on the catalyst surface rapidly dropped from 0.67 to 0.39, while the copper crystallite size remained almost unchanged. However, during the reaction period of 38–50 h, the Cu+/(Cu++Cu0) value possessed no distinct change, but a further decrease in ethanol selectivity and a rapid aggregation in Cu particles were observed simultaneously. The present systematic investigation demonstrated that the decrease of Cu+/(Cu++Cu0) value was the main factor for the loss of ethanol selectivity during the initial 38 h, whereas the rapid growth of Cu particles during the reaction period of 38–50 h were mainly contributed to the further decline of ethanol selectivity.

Synthesis, characterization, thermogravimetry, and structural study of uranium complexes derived from dibasic S-alkylated thiosemicarbazone ligands

Fasihizad, Ahad,Barak, Tahere,Ahmadi, Mehdi,Dusek, Michal,Pojarova, Michaela

, p. 2160 - 2170 (2014)

Two pentagonal bipyramidal complexes, ethanol-(S-ethyl-N1,N 4-bis(3-methoxy-2-hydroxybenzaldehyde)-isothiosemicarbazide-N,N',O, O')-dioxidouranium(VI) (1) and ethanol-(S-ethyl-N1-(2- hydroxyacetophenone)-N4-(5-bromo-2-hydroxybenzaldehyde)- isothiosemicarbazide-N,N',O,O')-dioxidouranium(VI) (2), have been prepared and characterized. Their structures have been determined by X-ray crystallography, and the structural parameters are discussed with those observed in related complexes. Electronic absorption, proton magnetic resonance, and FT-IR spectra have been recorded and analyzed. In both complexes, the U(VI) centers are surrounded by N2O2 donor ligands, two oxido groups, and one ethanol in a distorted pentagonal bipyramid. The thermal stability of the new complexes has also been determined. 2014

Lemay,Ouellet

, p. 1316 (1955)

Efficient methane electrocatalytic conversion over a Ni-based hollow fiber electrode

Chen, Wei,Dong, Xiao,Guo, Zhikai,Li, Guihua,Song, Yanfang,Sun, Yuhan,Wei, Wei

, p. 1067 - 1072 (2020)

Natural gas and shale gas, with methane as the main component, are important and clean fossil energy resources. Direct catalytic conversion of methane to valuable chemicals is considered a crown jewel topic in catalysis. Substantial studies on processes including methane reforming, oxidative coupling of methane, non-oxidative coupling of methane, etc. have been conducted for many years. However, owing to the intrinsic chemical inertness of CH4, harsh reaction conditions involving either extremely high temperatures or highly oxidative reactants are required to activate the C–H bonds of CH4 in such thermocatalytic processes, which may cause the target products, such as ethylene or methanol, to be further converted into coke or CO and CO2. It is desirable to adopt a new strategy for direct CH4 conversion under mild conditions. Herein, we report that efficient electrocatalytic oxidation of methane to alcohols at ambient temperature and pressure can be achieved using a NiO/Ni hollow fiber electrode. This work opens a new avenue for direct catalytic conversion of CH4.

Hydrogenation of carbon dioxide to methanol by using a homogeneous ruthenium-phosphine catalyst

Wesselbaum, Sebastian,Vom Stein, Thorsten,Klankermayer, Juergen,Leitner, Walter

, p. 7499 - 7502 (2012)

Simply efficient: The homogenously catalyzed hydrogenation of CO 2 to methanol is achieved by using a ruthenium phosphine complex under relatively mild conditions (see scheme; HNTf2= bis(trifluoromethane)sulfonimide). This is the first example of CO2 hydrogenation to methanol by using a single molecularly defined catalyst. Copyright

Nitric oxide as an activation agent for nucleophilic attack in trans-[Ru(NO)(NH3)4{P(OEt)3}](PF 6)3

Metzker, Gustavo,Toledo Jr., Jose? C.,Lima, Francisco C. A.,Magalha?es, Alvicler,Cardoso, Daniel R.,Franco, Douglas W.

, p. 1266 - 1273 (2010)

The complex trans-[Ru(NO)(NH3)4{P(OEt) 3}](PF6)3 undergoes nucleophilic attack on the phosphorus ester ligand in the solid state yielding trans-[Ru(NO)(NH 3)4{P(OH)(OEt)2/s

2-(4-Nitrophenyl)-1H-indolyl-3-methyl Chromophore: A Versatile Photocage that Responds to Visible-light One-photon and Near-infrared-light Two-photon Excitations

Abe, Manabu,Guo, Runzhao,Hamao, Kozue,Lin, Qianghua,Takagi, Ryukichi

supporting information, p. 153 - 156 (2022/02/14)

Due to cell damage caused by UV light, photoremovable protecting groups (PPGs) that are removed using visible or near-infrared light are attracting attention. A 2-(4-nitrophenyl)- 1H-indolyl-3-methyl chromophore (NPIM) was synthesized as a novel PPG. Various compounds were caged using this PPG and uncaged using visible or near-infrared light. Low cytotoxicity of NPIM indicates that it may be applied in physiological studies.

Nanoconfinement Engineering over Hollow Multi-Shell Structured Copper towards Efficient Electrocatalytical C?C coupling

Li, Jiawei,Liu, Chunxiao,Xia, Chuan,Xue, Weiqing,Zeng, Jie,Zhang, Menglu,Zheng, Tingting

supporting information, (2021/12/06)

Nanoconfinement provides a promising solution to promote electrocatalytic C?C coupling, by dramatically altering the diffusion kinetics to ensure a high local concentration of C1 intermediates for carbon dimerization. Herein, under the guidance of finite-element method simulations results, a series of Cu2O hollow multi-shell structures (HoMSs) with tunable shell numbers were synthesized via Ostwald ripening. When applied in CO2 electroreduction (CO2RR), the in situ formed Cu HoMSs showed a positive correlation between shell numbers and selectivity for C2+ products, reaching a maximum C2+ Faradaic efficiency of 77.0±0.3 % at a conversion rate of 513.7±0.7 mA cm?2 in a neutral electrolyte. Mechanistic studies clarified the confinement effect of HoMSs that superposition of Cu shells leads to a higher coverage of localized CO adsorbate inside the cavity for enhanced dimerization. This work provides valuable insights for the delicate design of efficient C?C coupling catalysts.

Efficient photocatalytic conversion of CH4into ethanol with O2over nitrogen vacancy-rich carbon nitride at room temperature

Yang, Zhongshan,Zhang, Qiqi,Ren, Liteng,Chen, Xin,Wang, Defa,Liu, Lequan,Ye, Jinhua

supporting information, p. 871 - 874 (2021/02/06)

A record ethanol production rate of 281.6 μmol g?1h?1for the photocatalytic conversion of methane over nitrogen vacancy-rich carbon nitride at room temperature was achieved. Systematic studies demonstrate that the CH4was activated by the highly reactive ˙OH radicals generated,viaH2O2, from the photo-reduction of O2with H2O.