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电催化还原二氧化碳制备甲酸是备受关注的热点问题。而电极材料是决定还原效率的重要因素。本文通过电沉积方法在泡沫铜上直接制备纳米结构硫化亚铜薄膜,并采用扫描电镜(SEM)、X射线衍射(XRD)对其结构性能进行了系统研究。以硫化亚铜作为阴极电催化材料、0.5 mol·L-1 1-丁基-3-甲基咪唑四氟硼酸盐的乙腈溶液为电解液,在该体系中可高效催化转化二氧化碳为甲酸。结果表明,这一电解体系可有效实现电化学反应,甲酸的法拉第效率(FEHCOOH)可以达到85%,同时甲酸还原电流密度可达到5.3 mA·cm-2。 相似文献
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过量化石能源的消耗导致大气中的二氧化碳含量不断上升,由此引发包括温室效应在内的环境问题。对此,常温常压下的电催化二氧化碳还原手段为制备高附加值的化工原料和实现碳循环提供了一种很有前景的技术储备。在众多的二氧化碳还原产物中,碳氢化合物尤其是乙烯,它作为塑料和其他化工产品的重要原料受到广泛的关注。电催化二氧化碳还原制乙烯工艺不仅可适配于现有的生产设备也可作为取代目前工业化的裂解方法。近年来,研究者们为了开发高效的电催化二氧化碳还原制乙烯催化剂开展了大量的研究。不过值得注意的是,大部分研究集中于铜基材料。尽管目前研究者取得了很多成果,但仍缺少可高选择性产乙烯的二氧化碳还原催化剂。如何设计出可活化二氧化碳分子,同时对*CO和*COH中间物有强吸附能力的催化剂是研究难点。针对此问题,本文中通过真空蒸镀的方法制备出一种富氧空位的非晶氧化铜纳米薄膜催化剂。受益于纳米薄膜的构建和氧空位的引入,该催化剂可快速进行电荷和物质的交换,并利于二氧化碳分子的吸附及优化还原中间产物的亲和力,进而表现出优异的电催化二氧化碳制乙烯的性能。结果表明,在加有0.1 mol·L-1碳酸氢钾溶液的H型电... 相似文献
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Metal‐Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons
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Dr. Ana Sofia Varela Dr. Nastaran Ranjbar Sahraie Julian Steinberg Wen Ju Dr. Hyung‐Suk Oh Prof. Dr. Peter Strasser 《Angewandte Chemie (International ed. in English)》2015,54(37):10758-10762
This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon‐based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low‐area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low‐cost, abundant electrocatalysts for synthetic fuel production from CO2. 相似文献
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Fucheng Gao Jian Huang Prof. Ying Ruan Prof. Hui Li Pengyu Gong Prof. Fenglong Wang Prof. Qunwei Tang Prof. Yanyan Jiang 《Angewandte Chemie (International ed. in English)》2023,62(7):e202214042
The lack of systematic structural resolution makes it difficult to build specific transition-metal-atom-doped carbonized polymer dots (TMA-doped CPDs). Herein, the structure-activity relationship between Cu atoms and CPDs was evaluated by studying the peroxidase-like properties of Glu−Cu−CPDs prepared by using copper glutamate (Glu) with a Cu−N2O2 initial structure. The results showed that the Cu atoms bound to Glu−Cu−CPDs in the form of Cu−N2C2, indicating that Cu−O bonds changed into Cu−C bonds under hydrothermal conditions. This phenomenon was also observed in other copper-doped CPDs. Moreover, the carboxyl and amino groups content decreased after copper-atom doping. Theoretical calculations revealed a dual-site catalytic mechanism for catalyzing H2O2. The detection of intracellular H2O2 suggested their application prospects. Our study provides an in-depth understanding of the formation and catalytic mechanism of TMA-doped-CPDs, allowing for the generation specific TMA-doped-CPDs. 相似文献
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用共沉淀法制备了不同M2+/M3+的层状双金属氢氧化物Zn(Cu)/Al-LDHs,利用粉末X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射(UV-Vis DRS)以及热重分析仪(TG-DSC)等测试方法表征了所制备样品的结构、形貌以及相关物性.在自行设计的催化反应系统中于室温和常压下测试了催化剂光催化还原CO2(g)+H2O(g)的活性.结果表明所制备的Zn(Cu)/Al-LDHs样品均可光催化还原CO2(g)+H2O(g),实验中测得的催化反应产物主要是CO和CH4.LDHs结构中Cu2+对Zn2+的取代导致催化剂吸收边红移,并显著提高催化反应产率. 相似文献
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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
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Jianyu Han Pengfei An Shuhu Liu Xiaofei Zhang Dawei Wang Yi Yuan Jun Guo Xueying Qiu Ke Hou Lin Shi Yin Zhang Shenlong Zhao Chang Long Zhiyong Tang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(36):12841-12846
The single‐site catalyst (SSC) characteristic of atomically dispersed active centers will not only maximize the catalytic activity, but also provide a promising platform for establishing the structure–activity relationship. However, arbitrary arrangements of active sites in the existed SSCs make it difficult for mechanism understanding and performance optimization. Now, a well‐defined ultrathin SSC is fabricated by assembly of metal‐porphyrin molecules, which enables the precise identification of the active sites for d‐orbital energy engineering. The activity of as‐assembled products for electrocatalytic CO2 reduction is significantly promoted via lifting up the energy level of metal d orbitals, exhibiting a remarkable Faradaic efficiency of 96 % at the overpotential of 500 mV. Furthermore, a turnover frequency of 4.21 s?1 is achieved with negligible decay over 48 h. 相似文献
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Mohana Shivanna Ken-ichi Otake Shotaro Hiraide Takao Fujikawa Ping Wang Yifan Gu Hirotaka Ashitani Shogo Kawaguchi Yoshiki Kubota Minoru T. Miyahara Susumu Kitagawa 《Angewandte Chemie (International ed. in English)》2023,62(39):e202308438
Porous sorbents are materials that are used for various applications, including storage and separation. Typically, the uptake of a single gas by a sorbent decreases with temperature, but the relative affinity for two similar gases does not change. However, in this study, we report a rare example of “crossover sorption,” in which the uptake capacity and apparent affinity for two similar gases reverse at different temperatures. We synthesized two soft porous coordination polymers (PCPs), [Zn2(L1)(L2)2]n (PCP-1) and [Zn2(L1)(L3)2]n (PCP-2) (L1= 1,4-bis(4-pyridyl)benzene, L2=5-methyl-1,3-di(4-carboxyphenyl)benzene, and L3=5-methoxy-1,3-di(4-carboxyphenyl)benzene). These PCPs exhibits structural changes upon gas sorption and show the crossover sorption for both C2H2/CO2 and C2H6/C2H4, in which the apparent affinity reverse with temperature. We used in situ gas-loading single-crystal X-ray diffraction (SCXRD) analysis to reveal the guest inclusion structures of PCP-1 for C2H2, CO2, C2H6, and C2H4 gases at various temperatures. Interestingly, we observed three-step single-crystal to single-crystal (sc-sc) transformations with the different loading phases under these gases, providing insight into guest binding positions, nature of host–guest or guest-guest interactions, and their phase transformations upon exposure to these gases. Combining with theoretical investigation, we have fully elucidated the crossover sorption in the flexible coordination networks, which involves a reversal of apparent affinity and uptake of similar gases at different temperatures. We discovered that this behaviour can be explained by the delicate balance between guest binding and host–guest and guest-guest interactions. 相似文献
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Wenyuan Lyu Dr. Yang Liu Jingyi Zhou Datong Chen Dr. Xin Zhao Dr. Ruiqi Fang Dr. Fengliang Wang Prof. Yingwei Li 《Angewandte Chemie (International ed. in English)》2023,62(42):e202310733
Photocatalytic conversion of low-concentration CO2 is considered as a promising way to simultaneously mitigate the environmental and energy issues. However, the weak CO2 adsorption and tough CO2 activation process seriously compromise the CO production, due to the chemical inertness of CO2 molecule and the formed fragile metal-C/O bond. Herein, we designed and fabricated oxygen vacancy contained Co3O4 hollow nanoparticles on ordered macroporous N-doped carbon framework (Vo−HCo3O4/OMNC) towards photoreduction of low-concentration CO2. In situ spectra and ab initio molecular dynamics simulations reveal that the constructed oxygen vacancy is able to break the local structural symmetry of Co−O−Co sites. The formation of asymmetric active site switches the CO2 configuration from a single-site linear model to a multiple-sites bending one with a highly stable configuration, enhancing the binding and structural polarization of CO2 molecules. As a result, Vo−HCo3O4/OMNC shows unprecedent activity in the photocatalytic conversion of low-concentration CO2 (10 % CO2/Ar) under laboratory light source or even natural sunlight, affording a syngas yield of 337.8 or 95.2 mmol g−1 h−1, respectively, with an apparent quantum yield up to 4.2 %. 相似文献
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FU Xinliang ZHU Aonan CHEN Xiaojie ZHANG Shifu WANG Mei YUAN Mingjian 《高等学校化学研究》2021,37(6):1328-1333
Electrocatalysis has become an attractive strategy for the artificial reduction of CO2 to high-value chemicals.However,the design and development of highly selective and stable non-noble metal electrocatalysts that convert CO2 to CO are still a challenge.As a new type of two-dimensional carbon material,graphdiyne(GDY),is rarely used to explore the application in carbon dioxide reduction reaction(CO2RR).Therefore,we tried to use GDY as a substrate to stabilize the copper-nickel alloy nanoparticles(NPs)to synthesize Cu/Ni@GDY.Cu/Ni@GDY requires an overpotential(-0.61 V)to 10 mA/cm2 for the formation of CO,and it shows better activity than Au and Ag,achieving a higher Faraday efficiency of about 95.2%and high stability of about 26 h at an overpotential(-0.70 V).The electronic interaction between GDY substrate and Cu/Ni alloy NPs and the large specific surface area of GDY is responsible for the high performance. 相似文献
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Yuxin Chen Lijun Wang Zhibo Yao Leiduan Hao Xinyi Tan Justus Masa Alex W. Robertson Zhenyu Sun 《物理化学学报》2023,38(11):2207024-0
The combustion of fossil fuels increases atmospheric carbon dioxide (CO2) concentrations, leading to adverse impacts on the planetary radiation balance and, consequently, on the climate. Fossil fuel utilization has contributed to a marked rise in global temperatures, now at least 1.2 ℃ above 'pre-industrial' levels. To meet the 2015 Paris Agreement target of 1.5 ℃ above pre-industrial levels, considerable efforts are required to efficiently capture and utilize CO2. Among the different strategies developed for converting CO2, electrochemical CO2 reduction (ECR) to valuable chemicals using renewable energy is expected to revolutionize the manufacture of sustainable "green" chemicals, thereby achieving a closed anthropogenic carbon cycle. However, CO2 is a thermodynamically stable and kinetically inert molecule that requires high electrical energy to bend the linear O=C=O bond by attacking the C atom. To facilitate the ECR with good energy efficiency, it is essential to lower the reaction overpotential as well as maintain a high current density and desirable product selectivity; therefore, the design and development of advanced electrocatalysts are crucial. A plethora of heterogeneous and homogeneous materials has been explored in the ECR. Among these materials, single-atom catalysts (SACs) have been the focus of most extensive research in the context of ECR. A SAC with isolated metal atoms dispersed on a supporting host exhibits a unique electronic structure, well-defined coordination environment, and an extremely high atom utilization maximum; thus, SACs have emerged as promising materials over the last two decades. Single-atom catalysis has covered the periodic table from d-block and ds-block metals to p-block metals. The types of support materials for SACs, ranging from metal oxides to tailored carbon materials, have also expanded. The adsorption strength and catalytic activity of SACs can be effectively tuned by modulating the central metal and local coordination structure of the SACs. In this article, we discuss the progress made to date in the field of single-atom catalysis for promoting ECR. We provide a comprehensive review of state-of-the-art SACs for the ECR in terms of product distribution, selectivity, partial current density, and performance stability. Special attention is paid to the modification of SACs to improve the ECR efficiency. This includes tailoring the coordination of the heteroatom, constructing bimetallic sites, engineering the morphologies and surface defects of supports, and regulating surface functional groups. The correlation of the coordination structure of SACs and metal-support interactions with ECR performance is analyzed. Finally, development opportunities and challenges for the application of SACs in the ECR, especially to form multi-carbon products, are presented.![]()
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电催化二氧化碳还原(ECR) 制备高值化学品被认为是在碳中和背景下实现可再生能源存储及降低CO2浓度的一种有效策略。为了实现此目标,催化剂的开发与设计是ECR研究的关键。单原子催化剂(SACs) 因其独特的电子结构、明确的配位环境和极高的原子利用率,近年来在ECR领域引起了广泛关注。通过调节SACs的中心金属元素种类和局部配位结构,可有效调节SACs对CO2和其还原中间体的吸附强度和催化活性。本文总结了SACs在ECR领域所取得的最新研究进展,重点讨论了SACs的配位结构及其与载体之间的相互作用对催化活性的影响以及相关调控策略,最后,提出了SACs应用于ECR所面临的机遇与挑战。 相似文献
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Xin Zi Yajiao Zhou Li Zhu Qin Chen Yao Tan Xiqing Wang Dr. Mahmoud Sayed Dr. Evangelina Pensa Dr. Ramadan A. Geioushy Dr. Kang Liu Dr. Junwei Fu Prof. Emiliano Cortés Prof. Min Liu 《Angewandte Chemie (International ed. in English)》2023,62(42):e202309351
Electrocatalytic CO2 reduction reaction (CO2RR) to multi-carbon products (C2+) in acidic electrolyte is one of the most advanced routes for tackling our current climate and energy crisis. However, the competing hydrogen evolution reaction (HER) and the poor selectivity towards the valuable C2+ products are the major obstacles for the upscaling of these technologies. High local potassium ions (K+) concentration at the cathode's surface can inhibit proton-diffusion and accelerate the desirable carbon-carbon (C−C) coupling process. However, the solubility limit of potassium salts in bulk solution constrains the maximum achievable K+ concentration at the reaction sites and thus the overall acidic CO2RR performance of most electrocatalysts. In this work, we demonstrate that Cu nanoneedles induce ultrahigh local K+ concentrations (4.22 M) – thus breaking the K+ solubility limit (3.5 M) – which enables a highly efficient CO2RR in 3 M KCl at pH=1. As a result, a Faradaic efficiency of 90.69±2.15 % for C2+ (FEC2+) can be achieved at 1400 mA.cm−2, simultaneous with a single pass carbon efficiency (SPCE) of 25.49±0.82 % at a CO2 flow rate of 7 sccm. 相似文献
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Zhen-Hua Zhao Jia-Run Huang Prof. Pei-Qin Liao Prof. Xiao-Ming Chen 《Angewandte Chemie (International ed. in English)》2023,62(22):e202301767
The development of efficient electrocatalysts with non-copper metal sites for electrochemical CO2 reduction reactions (eCO2RR) to hydrocarbons and oxygenates is highly desirable, but still a great challenge. Herein, a stable metal–organic framework (DMA)4[Sn2(THO)2] (Sn-THO, THO6− = triphenylene-2,3,6,7,10,11-hexakis(olate), DMA = dimethylammonium) with isolated and distorted octahedral SnO62− active sites is reported as an electrocatalyst for eCO2RR, showing an exceptional performance for eCO2RR to the CH4 product rather than the common products formate and CO for reported Sn-based catalysts. The partial current density of CH4 reaches a high value of 34.5 mA cm−2, surpassing most reported copper-based and all non-Cu metal-based catalysts. Our experimental and theoretical results revealed that the isolated SnO62− active site favors the formation of key *OCOH species to produce CH4 and can greatly inhibit the formation of *OCHO and *COOH species to produce *HCOOH and *CO, respectively. 相似文献
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Dr. Yang Yang Dr. Saira Ajmal Yiqing Feng Dr. Kejian Li Dr. Xiuzhen Zheng Prof. Liwu Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(18):4080-4089
It is still poorly understood how the first intermediates of CO2 reduction are formed and converted to multi-carbon products over Cu-based electrodes. Herein, Ag is used to decorate dendritic Cu and a high Faradaic efficiency (FE) for C2H4 (25 %) is obtained on a CuAg electrode, which is about five times higher than dendritic Cu. The intermediates including *CO2−, OH groups, Cu-CO, C-O rotation, and CHx species are investigated by in situ Raman spectroscopy. This work provides spectroscopic evidence that the first intermediate of CO2 reduction on Ag-decorated Cu is carboxylate anion *CO2− bonded with the catalyst surface through the C and O atom. The formation and evolution process of the *CO2− intermediate over the applied potential are investigated in depth as well. This research contributes to a better understanding of the mechanism of CO2 reduction and multi-carbon product formation pathways over Ag-decorated Cu. 相似文献
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David M. Koshy Dr. Shucheng Chen Dr. Dong Un Lee Dr. Michaela Burke Stevens Ahmed M. Abdellah Samuel M. Dull Gan Chen Dr. Dennis Nordlund Dr. Alessandro Gallo Dr. Christopher Hahn Dr. Drew C. Higgins Dr. Zhenan Bao Dr. Thomas F. Jaramillo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4072-4079
Ni,N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO2R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts. 相似文献
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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
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载体对镍基催化剂CH4/CO2重整制合成气性能的影响 总被引:7,自引:3,他引:7
在Ni/MgO、Ni/CaO和Ni/CeO催化剂上,CH4/CO2重整制事成的活性测试表明MgO是一种较好的载体,TPR实验显示,Ni-MgO之间的相互作用比Ni-CaO和Ni-CeO2强,现场CO岐化和CH4解离实验表明, 经剂表面吸附的氢会促进CO歧化和CH4解离积炭。 相似文献