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1.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(39):12013-12016
Photoelectrochemical (PEC) reduction of carbon dioxide (CO2) is a potential method for production of fuels and chemicals from a C1 feedstock accumulated in the atmosphere. However, the low solubility of CO2 in water, and complicated processes associated with capture and conversion, render CO2 conversion inefficient. A new concept is proposed in which a PEC system is used to capture and convert CO2 into formic acid. The process is assisted by an ionic liquid (1‐aminopropyl‐3‐methylimidazolium bromide) aqueous solution, which functions as an absorbent and electrolyte at ambient temperature and pressure. Within this PEC reduction strategy, the ionic liquid plays a critical role in promoting the conversion of CO2 to formic acid and suppressing the reduction of H2O to H2. At an applied voltage of 1.7 V, the Faradaic efficiency for formic acid production is as high as 94.1 % and the electro‐to‐chemical efficiency is 86.2 %. 相似文献
2.
Efficient Reduction of CO2 into Formic Acid on a Lead or Tin Electrode using an Ionic Liquid Catholyte Mixture
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Dr. Qinggong Zhu Dr. Jun Ma Xinchen Kang Xiaofu Sun Prof. Huizhen Liu Jiayin Hu Prof. Zhimin Liu Prof. Buxing Han 《Angewandte Chemie (International ed. in English)》2016,55(31):9012-9016
Highly efficient electrochemical reduction of CO2 into value‐added chemicals using cheap and easily prepared electrodes is environmentally and economically compelling. The first work on the electrocatalytic reduction of CO2 in ternary electrolytes containing ionic liquid, organic solvent, and H2O is described. Addition of a small amount of H2O to an ionic liquid/acetonitrile electrolyte mixture significantly enhanced the efficiency of the electrochemical reduction of CO2 into formic acid (HCOOH) on a Pb or Sn electrode, and the efficiency was extremely high using an ionic liquid/acetonitrile/H2O ternary mixture. The partial current density for HCOOH reached 37.6 mA cm?2 at a Faradaic efficiency of 91.6 %, which is much higher than all values reported to date for this reaction, including those using homogeneous and noble metal electrocatalysts. The reasons for such high efficiency were investigated using controlled experiments. 相似文献
3.
Reduction of Carbon Dioxide to Formate at Low Overpotential Using a Superbase Ionic Liquid
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Dr. Nathan Hollingsworth Dr. S. F. Rebecca Taylor Miguel T. Galante Dr. Johan Jacquemin Dr. Claudia Longo Dr. Katherine B. Holt Prof. Nora H. de Leeuw Prof. Christopher Hardacre 《Angewandte Chemie (International ed. in English)》2015,54(47):14164-14168
A new low‐energy pathway is reported for the electrochemical reduction of CO2 to formate and syngas at low overpotentials, utilizing a reactive ionic liquid as the solvent. The superbasic tetraalkyl phosphonium ionic liquid [P66614][124Triz] is able to chemisorb CO2 through equimolar binding of CO2 with the 1,2,4‐triazole anion. This chemisorbed CO2 can be reduced at silver electrodes at overpotentials as low as 0.17 V, forming formate. In contrast, physically absorbed CO2 within the same ionic liquid or in ionic liquids where chemisorption is impossible (such as [P66614][NTf2]) undergoes reduction at significantly increased overpotentials, producing only CO as the product. 相似文献
4.
Xiaofu Sun Chunjun Chen Shoujie Liu Song Hong Qinggong Zhu Qingli Qian Buxing Han Jing Zhang Lirong Zheng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4717-4721
Electrochemical reduction of CO2 into energy‐dense chemical feedstock and fuels provides an attractive pathway to sustainable energy storage and artificial carbon cycle. Herein, we report the first work to use atomic Ir electrocatalyst for CO2 reduction. By using α‐Co(OH)2 as the support, the faradaic efficiency of CO could reach 97.6 % with a turnover frequency (TOF) of 38290 h?1 in aqueous electrolyte, which is the highest TOF up to date. The electrochemical active area is 23.4‐times higher than Ir nanoparticles (2 nm), which is highly conductive and favors electron transfer from CO2 to its radical anion (CO2.?). Moreover, the more efficient stabilization of CO2.? intermediate and easy charge transfer makes the atomic Ir electrocatalyst facilitate CO production. Hence, α‐Co(OH)2‐supported atomic Ir electrocatalysts show enhanced CO2 activity and stability. 相似文献
5.
Hongwen Zhang Jintao Ming Jiwu Zhao Quan Gu Chao Xu Zhengxin Ding Rusheng Yuan Zizhong Zhang Huaxiang Lin Xuxu Wang Jinlin Long 《Angewandte Chemie (International ed. in English)》2019,58(23):7718-7722
An artificial photosynthetic (APS) system consisting of a photoanodic semiconductor that harvests solar photons to split H2O, a Ni‐SNG cathodic catalyst for the dark reaction of CO2 reduction in a CO2‐saturated NaHCO3 solution, and a proton‐conducting membrane enabled syngas production from CO2 and H2O with solar‐to‐syngas energy‐conversion efficiency of up to 13.6 %. The syngas CO/H2 ratio was tunable between 1:2 and 5:1. Integration of the APS system with photovoltaic cells led to an impressive overall quantum efficiency of 6.29 % for syngas production. The largest turnover frequency of 529.5 h?1 was recorded with a photoanodic N‐TiO2 nanorod array for highly stable CO production. The CO‐evolution rate reached a maximum of 154.9 mmol g?1 h?1 in the dark compartment of the APS cell. Scanning electrochemical–atomic force microscopy showed the localization of electrons on the single‐nickel‐atom sites of the Ni‐SNG catalyst, thus confirming that the multielectron reduction of CO2 to CO was kinetically favored. 相似文献
6.
Hongwen Zhang Jintao Ming Jiwu Zhao Quan Gu Chao Xu Zhengxin Ding Rusheng Yuan Zizhong Zhang Huaxiang Lin Xuxu Wang Jinlin Long 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(23):7800-7804
An artificial photosynthetic (APS) system consisting of a photoanodic semiconductor that harvests solar photons to split H2O, a Ni‐SNG cathodic catalyst for the dark reaction of CO2 reduction in a CO2‐saturated NaHCO3 solution, and a proton‐conducting membrane enabled syngas production from CO2 and H2O with solar‐to‐syngas energy‐conversion efficiency of up to 13.6 %. The syngas CO/H2 ratio was tunable between 1:2 and 5:1. Integration of the APS system with photovoltaic cells led to an impressive overall quantum efficiency of 6.29 % for syngas production. The largest turnover frequency of 529.5 h?1 was recorded with a photoanodic N‐TiO2 nanorod array for highly stable CO production. The CO‐evolution rate reached a maximum of 154.9 mmol g?1 h?1 in the dark compartment of the APS cell. Scanning electrochemical–atomic force microscopy showed the localization of electrons on the single‐nickel‐atom sites of the Ni‐SNG catalyst, thus confirming that the multielectron reduction of CO2 to CO was kinetically favored. 相似文献
7.
MoP Nanoparticles Supported on Indium‐Doped Porous Carbon: Outstanding Catalysts for Highly Efficient CO2 Electroreduction
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Xiaofu Sun Lu Lu Dr. Qinggong Zhu Dr. Congyi Wu Dexin Yang Chunjun Chen Prof. Dr. Buxing Han 《Angewandte Chemie (International ed. in English)》2018,57(9):2427-2431
Electrochemical reduction of CO2 into value‐added product is an interesting area. MoP nanoparticles supported on porous carbon were synthesized using metal–organic frameworks as the carbon precursor, and initial work on CO2 electroreduction using the MoP‐based catalyst were carried out. It was discovered that MoP nanoparticles supported on In‐doped porous carbon had outstanding performance for CO2 reduction to formic acid. The Faradaic efficiency and current density could reach 96.5 % and 43.8 mA cm?2, respectively, when using ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate as the supporting electrolyte. The current density is higher than those reported up to date with very high Faradaic efficiency. The MoP nanoparticles and the doped In2O3 cooperated very well in catalyzing the CO2 electroreduction. 相似文献
8.
Catalytic Reduction of CN−, CO,and CO2 by Nitrogenase Cofactors in Lanthanide‐Driven Reactions
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Dr. Chi Chung Lee Prof. Dr. Yilin Hu Prof. Dr. Markus W. Ribbe 《Angewandte Chemie (International ed. in English)》2015,54(4):1219-1222
Nitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN?), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6‐lutidinium triflate (Lut‐H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN? or CO to C1–C4 hydrocarbons, and CO2 to CO and C1–C3 hydrocarbons. The C? C coupling from CO2 indicates a unique Fischer–Tropsch‐like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN?, CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase‐based electrocatalysts for the production of hydrocarbons from these carbon‐containing compounds. 相似文献
9.
Chi Chung Lee Yilin Hu Markus W. Ribbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(4):1235-1238
Nitrogenase cofactors can be extracted into an organic solvent to catalyze the reduction of cyanide (CN−), carbon monoxide (CO), and carbon dioxide (CO2) without using adenosine triphosphate (ATP), when samarium(II) iodide (SmI2) and 2,6‐lutidinium triflate (Lut‐H) are employed as a reductant and a proton source, respectively. Driven by SmI2, the cofactors catalytically reduce CN− or CO to C1–C4 hydrocarbons, and CO2 to CO and C1–C3 hydrocarbons. The C C coupling from CO2 indicates a unique Fischer–Tropsch‐like reaction with an atypical carbonaceous substrate, whereas the catalytic turnover of CN−, CO, and CO2 by isolated cofactors suggests the possibility to develop nitrogenase‐based electrocatalysts for the production of hydrocarbons from these carbon‐containing compounds. 相似文献
10.
Melanie Miller William E. Robinson Ana Rita Oliveira Nina Heidary Nikolay Kornienko Julien Warnan Inês A. C. Pereira Erwin Reisner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(14):4649-4653
The integration of enzymes with synthetic materials allows efficient electrocatalysis and production of solar fuels. Here, we couple formate dehydrogenase ( FDH ) from Desulfovibrio vulgaris Hildenborough (DvH) to metal oxides for catalytic CO2 reduction and report an in‐depth study of the resulting enzyme–material interface. Protein film voltammetry (PFV) demonstrates the stable binding of FDH on metal‐oxide electrodes and reveals the reversible and selective reduction of CO2 to formate. Quartz crystal microbalance (QCM) and attenuated total reflection infrared (ATR‐IR) spectroscopy confirm a high binding affinity for FDH to the TiO2 surface. Adsorption of FDH on dye‐sensitized TiO2 allows for visible‐light‐driven CO2 reduction to formate in the absence of a soluble redox mediator with a turnover frequency (TOF) of 11±1 s?1. The strong coupling of the enzyme to the semiconductor gives rise to a new benchmark in the selective photoreduction of aqueous CO2 to formate. 相似文献
11.
Qinggong Zhu Dexin Yang Huizhen Liu Xiaofu Sun Chunjun Chen Jiahui Bi Jiyuan Liu Haihong Wu Buxing Han 《Angewandte Chemie (International ed. in English)》2020,59(23):8896-8901
Electrocatalytic reduction of CO2 to a single product at high current densities and efficiencies remains a challenge. However, the conventional electrode preparation methods, such as drop‐casting, usually suffer from low intrinsic activity. Herein, we report a synthesis strategy for preparing heterogeneous electrocatalyst composed of 3D hierarchical Cu dendrites that derived from an in situ electrosynthesized hollow copper metal–organic framework (MOF), for which the preparation of the Cu‐MOF film took only 5 min. The synthesis strategy preferentially exposes active sites, which favor's the reduction of CO2 to formate. The current density could be as high as 102.1 mA cm?2 with a selectivity of 98.2 % in ionic‐liquid‐based electrolyte and a commonly used H‐type cell. 相似文献
12.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(43):13478-13482
A novel strategy based on the concept of preorganization and cooperation has been designed for a superior capacity to capture low‐concentration CO2 by imide‐based ionic liquids. By using this strategy, for the first time, an extremely high gravimetric CO2 capacity of up to 22 wt % (1.65 mol mol−1) and excellent reversibility (16 cycles) have been achieved from 10 vol. % of CO2 in N2 when using an ionic liquid having a preorganized anion. Through a combination of quantum‐chemical calculations and spectroscopic investigations, it is suggested that cooperative interactions between CO2 and multiple active sites in the preorganized anion are the driving force for the superior CO2 capacity and excellent reversibility. 相似文献
13.
Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
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Dr. Peng Kang Dr. Sheng Zhang Prof. Thomas J. Meyer Prof. Maurice Brookhart 《Angewandte Chemie (International ed. in English)》2014,53(33):8709-8713
An iridium pincer dihydride catalyst was immobilized on carbon nanotube‐coated gas diffusion electrodes (GDEs) by using a non‐covalent binding strategy. The as‐prepared GDEs are efficient, selective, durable, gas permeable electrodes for electrocatalytic reduction of CO2 to formate. High turnover numbers (ca. 54 000) and turnover frequencies (ca. 15 s?1) were enabled by the novel electrode architecture in aqueous solutions saturated in CO2 with added HCO3?. 相似文献
14.
Controllable Synthesis of Few‐Layer Bismuth Subcarbonate by Electrochemical Exfoliation for Enhanced CO2 Reduction Performance
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Ying Zhang Xiaolong Zhang Yunzhi Ling Fengwang Li Prof. Alan M. Bond Dr. Jie Zhang 《Angewandte Chemie (International ed. in English)》2018,57(40):13283-13287
Two‐dimensional (2D) engineering of materials has been recently explored to enhance the performance of electrocatalysts by reducing their dimensionality and introducing more catalytically active ones. In this work, controllable synthesis of few‐layer bismuth subcarbonate nanosheets has been achieved via an electrochemical exfoliation method. These nanosheets catalyse CO2 reduction to formate with high faradaic efficiency and high current density at a low overpotential owing to the 2D structure and co‐existence of bismuth subcarbonate and bismuth metal under catalytic turnover conditions. Two underlying fast electron transfer processes revealed by Fourier‐transformed alternating current voltammetry (FTacV) are attributed to CO2 reduction at bismuth subcarbonate and bismuth metal. FTacV results also suggest that protonation of CO2.? is the rate determining step for bismuth catalysed CO2 reduction. 相似文献
15.
A Protic Ionic Liquid Catalyzes CO2 Conversion at Atmospheric Pressure and Room Temperature: Synthesis of Quinazoline‐2,4(1H,3H)‐diones
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Dr. Yanfei Zhao Bo Yu Dr. Zhenzhen Yang Dr. Hongye Zhang Leiduan Hao Xiang Gao Prof. Zhimin Liu 《Angewandte Chemie (International ed. in English)》2014,53(23):5922-5925
The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2‐reactive protic ionic liquid (PIL), [HDBU+][TFE?], was designed by neutralization of the superbase 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2‐aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline‐2,4(1H,3H)‐diones in excellent yields. 相似文献
16.
Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids
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Guangtong Zeng Jing Qiu Bingya Hou Haotian Shi Dr. Yongjing Lin Mark Hettick Prof. Ali Javey Prof. Stephen B. Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13502-13507
A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn‐junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99 % at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron‐hole pair recombination rate. NMR spectra show that the [EMIM]+ ions in solution form an intermediate complex with CO2?, thus lowering the energy barrier of this reaction. 相似文献
17.
Young‐Hoon Chung Min Gwan Ha Youngseung Na Hee‐Young Park Hyoung‐Juhn Kim Dirk Henkensmeier Sung Jong Yoo Jin Young Kim So Young Lee Seung Woo Lee Hyun S. Park Yong‐Tae Kim Jong Hyun Jang 《Electroanalysis》2019,31(7):1401-1408
The ability to capture, store, and use CO2 is important for remediating greenhouse‐gas emissions and combatting global warming. Herein, Au nanoparticles (Au‐NPs) are synthesized for effective electrochemical CO2 reduction and syngas production, using polyethylenimine (PEI) as a ligand molecule. The PEI‐assisted synthesis provides uniformly sized 3‐nm Au NPs, whereas larger irregularly shaped NPs are formed in the absence of PEI in the synthesis solution. The Au‐NPs synthesized with PEI (PEI?Au/C, average PEI Mw=2000) exhibit improved CO2 reduction activities compared to Au‐NPs formed in the absence of PEI (bare Au NPs/C). PEI?Au/C displays a 34 % higher activity toward CO2 reduction than bare Au NPs/C; for example, PEI?Au/C exhibits a CO partial current density (jCO) of 28.6 mA cm?2 at ?1.13 VRHE, while the value for bare Au NPs/C is 21.7 mA cm?2; the enhanced jCO is mainly due to the larger surface area of PEI?Au/C. Furthermore, the PEI?Au/C electrode exhibits stable performance over 64 h, with an hourly current degradation rate of 0.25 %. The developed PEI?Au/C is employed in a CO2‐reduction device coupled with an IrO2 water‐oxidation catalyst and a proton‐conducting perfluorinated membrane to form a PEI?Au/C|Nafion|IrO2 membrane‐electrode assembly. The device using PEI?Au/C as the CO2‐reduction catalyst exhibits a jCO of 4.47 mA/cm2 at 2.0 Vcell. Importantly, the resulted PEI?Au/C is appropriate for efficient syngas production with a CO ratio of around 30–50 %. 相似文献
18.
Jiong Wang Xiang Huang Shibo Xi Jong‐Min Lee Cheng Wang Yonghua Du Xin Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(38):13666-13673
Immobilization of planar CoII‐2,3‐naphthalocyanine (NapCo) complexes onto doped graphene resulted in a heterogeneous molecular Co electrocatalyst that was active and selective to reduce CO2 into CO in aqueous solution. A systematic study revealed that graphitic sulfoxide and carboxyl dopants of graphene were the efficient binding sites for the immobilization of NapCo through axial coordination and resulted in active Co sites for CO2 reduction. Compared to carboxyl dopants, the sulfoxide dopants further improved the electron communication between NapCo and graphene, which led to the increase of turnover frequency of the Co sites by about 3 times for CO production with a Faradic efficiency up to 97 %. Pristine NapCo in the absence of a graphene support did not display efficient electron communication with the electrode and thus failed to serve as the electrochemical active site for CO2 reduction under the identical conditions. 相似文献
19.
Jochen Fesseler Dr. Jae‐Hun Jeoung Prof. Dr. Holger Dobbek 《Angewandte Chemie (International ed. in English)》2015,54(29):8560-8564
Ni,Fe‐containing CO dehydrogenases (CODHs) use a [NiFe4S4] cluster, termed cluster C, to reversibly reduce CO2 to CO with high turnover number. Binding to Ni and Fe activates CO2, but current crystal structures have insufficient resolution to analyze the geometry of bound CO2 and reveal the extent and nature of its activation. The crystal structures of CODH in complex with CO2 and the isoelectronic inhibitor NCO? are reported at true atomic resolution (dmin≤1.1 Å). Like CO2, NCO? is a μ2,η2 ligand of the cluster and acts as a mechanism‐based inhibitor. While bound CO2 has the geometry of a carboxylate group, NCO? is transformed into a carbamoyl group, thus indicating that both molecules undergo a formal two‐electron reduction after binding and are stabilized by substantial π backbonding. The structures reveal the combination of stable μ2,η2 coordination by Ni and Fe2 with reductive activation as the basis for both the turnover of CO2 and inhibition by NCO?. 相似文献
20.
Dr. Xin Su Dr. Tobias Robert Sean M. Mercer Christine Humphries Prof. Dr. Michael F. Cunningham Prof. Dr. Philip G. Jessop 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(18):5595-5601
We have developed a new benign means of reversibly breaking emulsions and latexes by using “switchable water”, an aqueous solution of switchable ionic strength. The conventional surfactant sodium dodecyl sulfate (SDS) is not normally stimuli‐responsive when CO2 is used as the stimulus but becomes CO2‐responsive or “switchable” in the presence of a switchable water additive. In particular, changes in the air/water surface tension and oil/water interfacial tension can be triggered by addition and removal of CO2. A switchable water additive, N,N‐dimethylethanolamine (DMEA), was found to be an effective and efficient additive for the reversible reduction of interfacial tension and can lower the tension of the dodecane/water interface in the presence of SDS surfactant to ultra‐low values at very low additive concentrations. Switchable water was successfully used to reversibly break an emulsion containing SDS as surfactant, and dodecane as organic liquid. Also, the addition of CO2 and switchable water can result in aggregation of polystyrene (PS) latexes; the later removal of CO2 neutralizes the DMEA and decreases the ionic strength allowing for the aggregated PS latex to be redispersed and recovered in its original state. 相似文献