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1.
Changsheng Cao Dr. Dong-Dong Ma Dr. Jia-Fang Gu Xiuyuan Xie Dr. Guang Zeng Dr. Xiaofang Li Shu-Guo Han Prof. Qi-Long Zhu Prof. Xin-Tao Wu Prof. Qiang Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):15124-15130
Electrochemical reduction of CO2 to valuable fuels is appealing for CO2 fixation and energy storage. However, the development of electrocatalysts with high activity and selectivity in a wide potential window is challenging. Herein, atomically thin bismuthene (Bi-ene) is pioneeringly obtained by an in situ electrochemical transformation from ultrathin bismuth-based metal–organic layers. The few-layer Bi-ene, which possesses a great mass of exposed active sites with high intrinsic activity, has a high selectivity (ca. 100 %), large partial current density, and quite good stability in a potential window exceeding 0.35 V toward formate production. It even deliver current densities that exceed 300.0 mA cm−2 without compromising selectivity in a flow-cell reactor. Using in situ ATR-IR spectra and DFT analysis, a reaction mechanism involving HCO3− for formate generation was unveiled, which brings new fundamental understanding of CO2 reduction. 相似文献
2.
Lin Jia Hui Yang Jun Deng Junmei Chen Yuan Zhou Pan Ding Leigang Li Na Han Yanguang Li 《中国化学》2019,37(5):497-500
Electrocatalytic carbon dioxide reduction holds great promise for reducing the atmospheric CO2 level and alleviating the energy crisis. High‐performance electrocatalysts are often required in order to lower the high overpotential and expedite the sluggish reaction kinetics of CO2 electroreduction. Copper is a promising candidate metal. However, it usually suffers from the issues of poor stability and low product selectivity. In this work, bimetallic Cu‐Bi is obtained by reducing the microspherical copper bismuthate (CuBi2O4) for selectively catalyzing the CO2 reduction to formate (HCOO–). The bimetallic Cu‐Bi electrocatalyst exhibits high activity and selectivity with the Faradic efficiency over 90% in a wide potential window. A maximum Faradaic efficiency of ~95% is obtained at –0.93 V versus reversible hydrogen electrode. Furthermore, the catalyst shows high stability over 6 h with Faradaic efficiency of ~95%. This study provides an important clue in designing new functional materials for CO2 electroreduction with high activity and selectivity. 相似文献
3.
Zaiqi Li Bin Sun Difei Xiao Prof. Zeyan Wang Prof. Yuanyuan Liu Prof. Zhaoke Zheng Prof. Peng Wang Prof. Ying Dai Prof. Hefeng Cheng Prof. Baibiao Huang 《Angewandte Chemie (International ed. in English)》2023,62(11):e202217569
Electrochemical CO2 reduction reaction (CO2RR) to chemical fuels such as formate offers a promising pathway to carbon-neutral future, but its practical application is largely inhibited by the lack of effective activation of CO2 molecules and pH-universal feasibility. Here, we report an electronic structure manipulation strategy to electron-rich Bi nanosheets, where electrons transfer from Cu donor to Bi acceptor in bimetallic Cu−Bi, enabling CO2RR towards formate with concurrent high activity, selectivity and stability in pH-universal (acidic, neutral and alkaline) electrolytes. Combined in situ Raman spectra and computational calculations unravel that electron-rich Bi promotes CO2⋅− formation to activate CO2 molecules, and enhance the adsorption strength of *OCHO intermediate with an up-shifted p-band center, thus leading to its superior activity and selectivity of formate. Further integration of the robust electron-rich Bi nanosheets into III–V-based photovoltaic solar cell results in an unassisted artificial leaf with a high solar-to-formate (STF) efficiency of 13.7 %. 相似文献
4.
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
5.
Peilin Deng Fan Yang Zhitong Wang Shenghua Chen Yinzheng Zhou Shahid Zaman Bao Yu Xia 《Angewandte Chemie (International ed. in English)》2020,59(27):10807-10813
Carbon dioxide (CO2) conversion is promising in alleviating the excessive CO2 level and simultaneously producing valuables. This work reports the preparation of carbon nanorods encapsulated bismuth oxides for the efficient CO2 electroconversion toward formate production. This resultant catalyst exhibits a small onset potential of ?0.28 V vs. RHE and partial current density of over 200 mA cm?2 with a stable and high Faradaic efficiency of 93 % for formate generation in a flow cell configuration. Electrochemical results demonstrate the synergistic effect in the Bi2O3@C promotes the rapid and selective CO2 reduction in which the Bi2O3 is beneficial for improving the reaction kinetics and formate selectivity, while the carbon matrix would be helpful for enhancing the activity and current density of formate production. This work provides effective bismuth‐based MOF derivatives for efficient formate production and offers insights in promoting practical CO2 conversion technology. 相似文献
6.
The reduction of carbon dioxide (CO2) into value-added fuels using an electrochemical method has been regarded as a compelling sustainable energy conversion technology. However, high-performance electrocatalysts for CO2 reduction reaction (CO2RR) with high formate selectivity and good stability need to be improved. Earth-abundant Bi has been demonstrated to be active for CO2RR to formate. Herein, we fabricated an extremely active and selective bismuth nanosheet (Bi-NSs) assembly via an in situ electrochemical transformation of (BiO)2CO3 nanostructures. The as-prepared material exhibits high activity and selectivity for CO2RR to formate, with nearly 94% faradaic efficiency at −1.03 V (versus reversible hydrogen electrode (vs. RHE)) and stable selectivity (>90%) in a large potential window ranging from −0.83 to −1.18 V (vs. RHE) and excellent durability during 12 h continuous electrolysis. In addition, the Bi-NSs based CO2RR/methanol oxidation reaction (CO2RR/MOR) electrolytic system for overall CO2 splitting was constructed, evidencing the feasibility of its practical implementation. 相似文献
7.
Jun‐Hao Zhou Kun Yuan Liang Zhou Yu Guo Ming‐Yu Luo Xiao‐Yan Guo Qing‐Yuan Meng Ya‐Wen Zhang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14335-14339
Bimetal‐S‐O composites have been rarely researched in electrochemical reduction of CO2. Now, an amorphous Ag‐Bi‐S‐O decorated Bi0 catalyst derived from Ag0.95BiS0.75O3.1 nanorods by electrochemical pre‐treatment was used for catalyzing eCO2RR, which exhibited a formate FE of 94.3 % with a formate partial current density of 12.52 mA cm?2 at an overpotential of only 450 mV. This superior performance was attributed to the attached amorphous Ag‐Bi‐S‐O substance. S could be retained in the amorphous region after electrochemical pre‐treatment only in samples derived from metal‐S‐O composites, and it would greatly enhance the formate selectivity by accelerating the dissociation of H2O. The existence of Ag would increase the current density, resulting in a higher local pH, which made the role of S in activating H2O more significantly and suppressed H2 evolution more effectively, thus endowing the catalyst with a higher formate FE at low overpotentials. 相似文献
8.
Dr. Wonhee Lee Young Eun Kim Dr. Min Hye Youn Dr. Soon Kwan Jeong Dr. Ki Tae Park 《Angewandte Chemie (International ed. in English)》2018,57(23):6883-6887
Electrochemical reduction of carbon dioxide (CO2) into value‐added chemicals is a promising strategy to reduce CO2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO2 reduction (CO2R) is the low solubility of CO2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte‐free electrocatalytic CO2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm?2, despite the decrease in CO2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L?1 is obtained as a one‐path product at 343 K with high PCD (51.7 mA cm?2) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. 相似文献
9.
Luocai Yi Dr. Junxiang Chen Ping Shao Dr. Junheng Huang Xinxin Peng Junwei Li Dr. Genxiang Wang Chi Zhang Prof. Zhenhai Wen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20287-20294
Two-dimensional (2D) monometallic pnictogens (antimony or Sb, and bismuth or Bi) nanosheets demonstrate potential in a variety of fields, including quantum devices, catalysis, biomedicine and energy, because of their unique physical, chemical, electronic and optical properties. However, the development of general and high-efficiency preparative routes toward high-quality pnictogen nanosheets is challenging. A general method involving a molten-salt-assisted aluminothermic reduction process is reported for the synthesis of Sb and Bi nanosheets in high yields (>90 %). Electrocatalytic CO2 reduction was investigated on the Bi nanosheets, and high catalytic selectively to formate was demonstrated with a considerable current density at a low overpotential and an impressive stability. Bi nanosheets continuously convert CO2 into formate in a flow cell operating for one month, with a yield rate of 787.5 mmol cm−2 h−1. Theoretical results suggest that the edge sites of Bi are far more active than the terrace sites. 相似文献
10.
Molybdenum–Bismuth Bimetallic Chalcogenide Nanosheets for Highly Efficient Electrocatalytic Reduction of Carbon Dioxide to Methanol
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Xiaofu Sun Dr. Qinggong Zhu Xinchen Kang Prof. Dr. Huizhen Liu Dr. Qingli Qian Dr. Zhaofu Zhang Prof. Dr. Buxing Han 《Angewandte Chemie (International ed. in English)》2016,55(23):6771-6775
Methanol is a very useful platform molecule and liquid fuel. Electrocatalytic reduction of CO2 to methanol is a promising route, which currently suffers from low efficiency and poor selectivity. Herein we report the first work to use a Mo‐Bi bimetallic chalcogenide (BMC) as an electrocatalyst for CO2 reduction. By using the Mo‐Bi BMC on carbon paper as the electrode and 1‐butyl‐3‐methylimidazolium tetrafluoroborate in MeCN as the electrolyte, the Faradaic efficiency of methanol could reach 71.2 % with a current density of 12.1 mA cm?2, which is much higher than the best result reported to date. The superior performance of the electrode resulted from the excellent synergistic effect of Mo and Bi for producing methanol. The reaction mechanism was proposed and the reason for the synergistic effect of Mo and Bi was discussed on the basis of some control experiments. This work opens a way to produce methanol efficiently by electrochemical reduction of CO2. 相似文献
11.
Peilin Deng Fan Yang Zhitong Wang Shenghua Chen Yinzheng Zhou Shahid Zaman Prof. Dr. Bao Yu Xia 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10899-10905
Carbon dioxide (CO2) conversion is promising in alleviating the excessive CO2 level and simultaneously producing valuables. This work reports the preparation of carbon nanorods encapsulated bismuth oxides for the efficient CO2 electroconversion toward formate production. This resultant catalyst exhibits a small onset potential of −0.28 V vs. RHE and partial current density of over 200 mA cm−2 with a stable and high Faradaic efficiency of 93 % for formate generation in a flow cell configuration. Electrochemical results demonstrate the synergistic effect in the Bi2O3@C promotes the rapid and selective CO2 reduction in which the Bi2O3 is beneficial for improving the reaction kinetics and formate selectivity, while the carbon matrix would be helpful for enhancing the activity and current density of formate production. This work provides effective bismuth-based MOF derivatives for efficient formate production and offers insights in promoting practical CO2 conversion technology. 相似文献
12.
Dr. Qinggong Zhu Dexin Yang Prof. Dr. Huizhen Liu Xiaofu Sun Chunjun Chen Jiahui Bi Jiyuan Liu Prof. Dr. Haihong Wu Prof. Dr. Buxing Han 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8981-8986
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
13.
Linghong Zhang Di Zhu Prof. Gilbert M. Nathanson Prof. Robert J. Hamers 《Angewandte Chemie (International ed. in English)》2014,53(37):9746-9750
Reduction of CO2 by direct one‐electron activation is extraordinarily difficult because of the ?1.9 V reduction potential of CO2. Demonstrated herein is reduction of aqueous CO2 to CO with greater than 90 % product selectivity by direct one‐electron reduction to CO2.? by solvated electrons. Illumination of inexpensive diamond substrates with UV light leads to the emission of electrons directly into water, where they form solvated electrons and induce reduction of CO2 to CO2.?. Studies using diamond were supported by studies using aqueous iodide ion (I?), a chemical source of solvated electrons. Both sources produced CO with high selectivity and minimal formation of H2. The ability to initiate reduction reactions by emitting electrons directly into solution without surface adsorption enables new pathways which are not accessible using conventional electrochemical or photochemical processes. 相似文献
14.
Regulation of Coordination Number over Single Co Sites: Triggering the Efficient Electroreduction of CO2
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Xiaoqian Wang Zhao Chen Xuyan Zhao Prof. Tao Yao Prof. Wenxing Chen Prof. Rui You Changming Zhao Geng Wu Jing Wang Prof. Weixin Huang Prof. Jinlong Yang Prof. Xun Hong Prof. Shiqiang Wei Prof. Yuen Wu Prof. Yadong Li 《Angewandte Chemie (International ed. in English)》2018,57(7):1944-1948
The design of active, selective, and stable CO2 reduction electrocatalysts is still challenging. A series of atomically dispersed Co catalysts with different nitrogen coordination numbers were prepared and their CO2 electroreduction catalytic performance was explored. The best catalyst, atomically dispersed Co with two‐coordinate nitrogen atoms, achieves both high selectivity and superior activity with 94 % CO formation Faradaic efficiency and a current density of 18.1 mA cm?2 at an overpotential of 520 mV. The CO formation turnover frequency reaches a record value of 18 200 h?1, surpassing most reported metal‐based catalysts under comparable conditions. Our experimental and theoretical results demonstrate that lower a coordination number facilitates activation of CO2 to the CO2.? intermediate and hence enhances CO2 electroreduction activity. 相似文献
15.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(11):2993-2997
Controlling the selectivity in electrochemical CO2 reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non‐precious catalyst for CO2 electroreduction, most Sn‐based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO2 reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra‐small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix. 相似文献
16.
Densely Packed,Ultra Small SnO Nanoparticles for Enhanced Activity and Selectivity in Electrochemical CO2 Reduction
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Dr. Jun Gu Dr. Florent Héroguel Prof. Dr. Jeremy Luterbacher Prof. Dr. Xile Hu 《Angewandte Chemie (International ed. in English)》2018,57(11):2943-2947
Controlling the selectivity in electrochemical CO2 reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non‐precious catalyst for CO2 electroreduction, most Sn‐based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO2 reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra‐small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix. 相似文献
17.
Lingxiang Wang Dr. Liang Wang Jian Zhang Xiaolong Liu Hai Wang Prof. Wei Zhang Qi Yang Jingyuan Ma Xue Dong Seung Jo Yoo Dr. Jin‐Gyu Kim Xiangju Meng Prof. Feng‐Shou Xiao 《Angewandte Chemie (International ed. in English)》2018,57(21):6104-6108
Methods for the hydrogenation of CO2 into valuable chemicals are in great demand but their development is still challenging. Herein, we report the selective hydrogenation of CO2 into ethanol over non‐noble cobalt catalysts (CoAlOx), presenting a significant advance for the conversion of CO2 into ethanol as the major product. By adjusting the composition of the catalysts through the use of different prereduction temperatures, the efficiency of CO2 to ethanol hydrogenation was optimized; the catalyst reduced at 600 ° gave an ethanol selectivity of 92.1 % at 140 °C with an ethanol time yield of 0.444 mmol g?1 h?1. Operando FT‐IR spectroscopy revealed that the high ethanol selectivity over the CoAlOx catalyst might be due to the formation of acetate from formate by insertion of *CHx, a key intermediate in the production of ethanol by CO2 hydrogenation. 相似文献
18.
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
19.
Divya Bohra Isis Ledezma‐Yanez Guanna Li Wiebren deJong Evgeny A. Pidko Wilson A. Smith 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1359-1363
Ag is a promising catalyst for the production of carbon monoxide (CO) via the electrochemical reduction of carbon dioxide (CO2ER). Herein, we study the role of the formate (HCOO?) intermediate *OCHO, aiming to resolve the discrepancy between the theoretical understanding and experimental performance of Ag. We show that the first coupled proton‐electron transfer (CPET) step in the CO pathway competes with the Volmer step for formation of *H, whereas this Volmer step is a prerequisite for the formation of *OCHO. We show that *OCHO should form readily on the Ag surface owing to solvation and favorable binding strength. In situ surface‐enhanced Raman spectroscopy (SERS) experiments give preliminary evidence of the presence of O‐bound bidentate species on polycrystalline Ag during CO2ER which we attribute to *OCHO. Lateral adsorbate interactions in the presence of *OCHO have a significant influence on the surface coverage of *H, resulting in the inhibition of HCOO? and H2 production and a higher selectivity towards CO. 相似文献
20.
Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi2O3 Nanosheets for Electrochemical Reduction of CO2 in a Wide Negative Potential Region
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Zhipeng Chen Kaiwen Mou Xiaohan Wang Prof. Licheng Liu 《Angewandte Chemie (International ed. in English)》2018,57(39):12790-12794
Large numbers of catalysts have been developed for the electrochemical reduction of CO2 to value‐added liquid fuels. However, it remains a challenge to maintain a high current efficiency in a wide negative potential range for achieving a high production rate of the target products. Herein, we report a 2D/0D composite catalyst composed of bismuth oxide nanosheets and nitrogen‐doped graphene quantum dots (Bi2O3‐NGQDs) for highly efficient electrochemical reduction of CO2 to formate. Bi2O3‐NGQDs demonstrates a nearly 100 % formate Faraday efficiency (FE) at a moderate overpotential of 0.7 V with a good stability. Strikingly, Bi2O3‐NGQDs exhibit a high activity (average formate FE of 95.6 %) from ?0.9 V to ?1.2 V vs. RHE. Additionally, DFT calculations reveal that the origin of enhanced activity in this wide negative potential range can be attributed to the increased adsorption energy of CO2(ads) and OCHO* intermediate after combination with NGQDs. 相似文献