Catalysts
·
2023
·Vol. 13
·期 5
·857
·
IF 3.9
Qianqian Zhou,Yanxin Chen,Haoyan Shi,Rui Chen,Minghao Ji,Kexian Li,Hailong Wang,Xia Jiang,Canzhong Lu
Cu2O is a p-type direct bandgap semiconductor with a band gap of 2~2.2 eV, which has excellent visible light absorption and utilization. However, slow charge transfer and poor stability hinder its practical application. In this paper, a facile electrodeposition approach successfully synthesized the heterostructure of p-Cu2O and n-Cu2O. The protective layer of n-Cu2O on the surface of p-Cu2O nanoparticles forms a p/n heterojunction. Due to the p/n heterojunction, the PEC performance of p/n-Cu2O is enhanced significantly. The charge separation efficiency of photogenerated electron/hole pairs in p/n-Cu2O is greatly improved. Therefore, p/n-Cu2O shows superior photoelectrochemical (PEC) CO2reduction reaction (CO2RR) efficiency when used as a photocathode.Keywords:Cu2O;electrodeposition;p/n heterojunction;carbon dioxide reduction reaction
研究领域:
材料科学
·
环境科学
✓ 已验证
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Fangfang Cai,Xia Hu,Faliang Gou,Yuyuan Chen,Yulu Xu,Chenze Qi,De-Kun Ma
Ternary ZnIn 2 S 4 (ZIS) is a kind of potential electrocatalyst for CO 2 reduction reaction (CO 2 RR). However, the reported reduction products are usual C1 species. Considering that N doped carbon can increase adsorption of CO 2 molecules, facilitate electron transfer, and activate active sites, here ultrathin ZIS nanosheet arrays (ZIS NSAs) grown on N doped carbon cloth (NDCC) were synthesized through a facile hydrothermal route. The as-synthesized ZIS NSAs/NDCC enabled electrocatalytic CO 2 RR toward ethanol with the highest 42 % faradaic efficiency (FE) at an applied potential of − 0.7 V versus the reversible hydrogen electrode (RHE) in CO 2 -saturated 0.5 M KHCO 3 aqueous solution. This is first report on ZIS-based electrocatalyst for electrocatalytic CO 2 RR toward ethanol production. The experimental results and density functional theory (DFT) calculations showed that NDCC could enhance the CO 2 RR activity and promote CO-CO coupling process. Our work not only provides a new electrocatalyst for CO 2 RR to ethanol but also stresses the influence of N doped carbon substrate and bimetallic effect on electrocatalytic CO 2 RR.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2025
·
IF 9.2
Xueqi Liu,Jingmin Ge,Shiying Li,Huanhuan Yang,Huiwen Tian,Hongpo Liu,Yaxi Li,Xiaoli Zheng,Yapeng Tian,Xinwei Cui,Qun Xu
Identification of the active sites for zinc oxide-derived catalysts and further elucidation of the catalytic mechanism for electrochemical CO2 reduction reaction (CO2RR) are limited by the dynamic structural evolution at real reaction conditions. Herein, we focus on the structural evolution of ZnO-T at the initial stage of CO2RR. ZnO-T undergoes in situ reduction to Zn within dozens of minutes, which is followed by reoxidation of the out layer. As a result, core-shell-like Zn@ZnO-T with controllable Zn-ZnO interfaces and oxygen vacancies is obtained depending on the temperature-controlled annealing and electrochemical pre-treatment. Zn-ZnO interfaces alter the energy band structure of ZnO layer, while oxygen vacancies modify the electron density of Zn sites. Thus, the obtained Zn@ZnO-T improves charge transfer, facilitates CO2 activation, and lowers energy barrier for *COOH and *CO intermediates formation. Expectedly, Zn@ZnO-T demonstrates excellent CO2RR performance for CO production with FE up to 92.1% at −1.2 V (vs. RHE) and a current density of −12.7 mA∙cm−2. In particular, Zn@ZnO-650 delivers a high FECO above 85% over a wide potential range from −1.0 to −1.3V (vs. RHE). This study provides a new compass for mechanistic investigation on relationship between intrinsic structure and catalytic performances, guiding the rational design of high-performance heterogeneous catalysts.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Xiaodong Zhang,Yajiao Zhou,Hang Zhang,HuangJingWei Li,Kang Liu,Hongmei Li,Hao Pan,Junhua Hu,Junwei Fu,Shanyong Chen,Min Liu
Formate is an important liquid chemical, which can be produced by electrocatalytic carbon dioxide reduction reaction (CO 2 RR). Most of the metal catalysts for CO 2 RR to formate are toxic or noble metals, such as Cd, Hg, Pb and Pd, leading to the environmental pollution or increased production costs. Herein, we develop an environmentally friendly and low-cost NiZn alloy catalyst for CO 2 RR to formate. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) confirm the alloy structure of the prepared NiZn catalyst. As for a catalyst for CO 2 RR, the NiZn alloy exhibits the FE HCOO - (Faraday efficiency of HCOO – ) of 36 ± 0.7% at − 0.9 V vs. RHE in 0.1 M KHCO 3 , and remarkable stability for 40,000 s at − 0.8, −0.9, −1.0 and − 1.1 V vs. RHE, respectively. Theoretical calculation results indicate that the NiZn alloy exhibits the middle valence electron structure between the Zn and Ni metal, resulting in the favorable pathway for HCOOH formation but unfavorable for the hydrogen evolution reaction and CO production. The Ultraviolet Photoelectron Spectroscopy results verify the modulated valence electron structure for NiZn alloy as compared to Ni and Zn, consistent with the theoretical calculation results. This work provides new insights into design of alloy catalysts for CO 2 RR to formate.
研究领域:
电化学
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催化材料
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理论计算
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Jing-Jing Ma,Hong-Lin Zhu,Yue-Qing Zheng,Miao Shui
Electrochemical CO2 reduction into CO with metal phthalocyanines/substrate catalysts has been receiving extensive attention due to unique activities and tunability. However, the anchoring sites and reaction mechanism still remain much debatable. In this work, through integrations of Raman spectroscopy with theoretical calculations, the anchoring location site and mechanism of CoPc on substrates were confirmed using cobalt phthalocyanine on acetylene black as model catalysts. The theoretical calculations show that the resultant CoPc/C catalyst exhibits an excellent catalytic activity for electrocatalytic CO2 reduction with low overpotential and high selectivity of CO because the defect beneath the benzene ring is more effective in anchoring CoPc.
研究领域:
化学
·
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Weiting Yu,Zhe Yang,Rendan Zhu,Mengzhi Lu,Tingjiang Lu,Yan Yu,Shuang Song
The photo-assisted electrochemical CO 2 reduction reaction (CO 2 RR) toward CO stands as a highly promising pathway for addressing environmental challenges and produces valuable chemicals. In this study, a novel pl-Si/Ag/Pc electrode was developed with the surface enveloped by an amorphous phthalocyanine overlayer. The pl-Si/Ag/Pc electrode has gained recognition as a catalyst of exceptional quality, displaying superior activity, selectivity toward CO, and stability. A synergistic mechanism has been revealed from experimental results that Ag served as active centers for CO 2 RR, Pc facilitated CO 2 adsorption and suppressed the competing HER reaction. Functionalizing the surface of electrode with Pc enhanced the CO selectivity (FE CO at 90.8 % under −1.5 V vs RHE) during the CO 2 RR process and reduced the cost in following product separation procedures. This study presents an uncomplicated yet effective approach for formulating durable and discerning electrocatalysts dedicated to the utilization of CO 2 .
研究领域:
材料科学
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环境科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTENGCOMM
·
2024
·Vol. 26
·期 48
·6844-6851
·
IF 2.6
Yuyuan Chen,Yachang Huang,Xia Hu,Sijie Lin,De-Kun Ma
The exposed crystal facets of Cu have a profound effect on its electrocatalytic CO2 reduction reaction (CO2RR) activity and product selectivity. On the other hand, at present, most of the studies on Cu-based electrocatalysts for the CO2RR focus on the synthesis of C2+ products. There are only a few reports involving methanol (CH3OH) generation over Cu nanocrystals. Herein, CuO nanosheets (NSs) and nanorods (NRs) were synthesized through a controlled oxidation and dehydration route under mild reaction conditions, using Cu mesh as a Cu source and conductive substrate, respectively. The as-synthesized CuO NSs and NRs were further converted into Cu NSs and NRs through an in situ electrochemical reduction method, respectively. The experimental results showed that CH3OH could be efficiently produced over Cu NSs with abundant (111) crystal facets through the electrocatalytic CO2RR. The maximum CH3OH faradaic efficiency (FE) obtained on Cu NSs is 68% at a relatively low applied potential of −0.6 V vs. reversible hydrogen electrode (RHE), which is 1.6 times larger than that achieved on Cu NRs with primarily exposed (200) crystal facets (42%). The crystal facet-dependent electrocatalytic CO2RR activity toward CH3OH production was elucidated based on theoretical calculations combined with experimental results.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Canyan Yang,Ruichen Wang,Chao Yu,Jinhua Xiao,Zhiwei Huang,Bihong Lv,Huawang Zhao,Xiaomin Wu,Guohua Jing
Cu-based catalysts inevitably undergo surface reconstruction during the electrochemical carbon dioxide reduction reaction (CO 2 RR) process. Thus, it is a challenge to construct stable Cu + -Cu 0 sites of Cu-based catalysts. In this study, we report a simple and facile engineering strategy for stable Cu + -Cu 0 sites and oxygen defects derived from the boron-doped copper composite catalyst (B-Cu x O) as an efficient CO 2 RR electrocatalyst. The 5 % B-Cu x O exhibited 48.44 % C 2+ products Faraday efficiency (FE) for 12 h at −1.0 V vs reversible hydrogen electrode (RHE) in H-cell, which was far superior to Cu x O (23.85 %). Combining density functional theory (DFT) and in situ Attenuated Total Reflection Fourier Transform Infrared spectroscopy ( in situ ATR-FTIR), a higher electronic depletion on the catalyst surface inhibited the electrons accumulation around Cu sites, thereby maintaining the positive charge and inhibiting the complete reduction of Cu + . Moreover, the high oxygen defects in 5 % B-Cu x O could effectively activate CO 2 into *CO. We emphasized that Cu + functioned as the primary active site by facilitating adsorption and dimerization of *CO, whereas Cu 0 assisted in optimizing CO 2 activation.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-14
·
IF 14.7
Liu Shikai,Li Yuheng,Wang Di,Xi Shibo,Xu Haoming,Wang Yulin,Li Xinzhe,Zang Wenjie,Liu Weidong,Su Mengyao,Yan Katherine,Nielander Adam C.,Wong Andrew B.,Lu Jiong,Jaramillo Thomas F.,Wang Lei,Canepa Pieremanuele,He Qian
The reconstruction of Cu catalysts during electrochemical reduction of CO 2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO 2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value ( e.g ., −0.4 V RHE when using 0.1 M KHCO 3 ). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO 2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Catalysis Science & Technology
·
2024
·
IF 4.4
Huangdong Wang,Zhihua Guo,Heng Zhang,Lin Jia,Min Sun,Lifeng Han,Haorun Li,Yan Guo,Shanghong Zeng
Arranging the active ingredients on the support surface at the molecular or atomic scale to create high-selectivity sites for the electrocatalytic CO2 reduction reaction (CO2RR) holds great promise, which is highly challenging. In this study, we report a strategy for constructing a bimetallic Ag–Ni electrocatalyst with Ni nanoparticles for H2O dissociation, as well as Ni atoms in the carbon skeleton and Ag nanoparticles on the surface for the CO2RR. These sites synergistically enable high selectivity for improving the conversion of CO2 to CO. Specifically, the FECO reaches 99.3% on Ag–Ni/CB at −0.8 V vs. RHE, and its FECO can be maintained over 95.8% in the potential range from −0.8 to −1.1 V vs. RHE. Our research presents an approach for alignment of bifunctional two-component active sites on the surface of a carbon support.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2024
·
IF 6.3
Xin Zhao,Genyan Hao,Qiang Fang,Xuelei Lang,Dandan Li,Dazhong Zhong,Jinping Li,Qiang Zhao
Copper (Cu) electrocatalysts for carbon dioxide reduction reaction (CO 2 RR) have attracted much attention due to their ability to produce high value-added C 2+ products (e.g., C 2 H 4 , C 2 H 5 OH, and n-propanol). However, achieving high selectivity of Cu electrocatalysts for C 2 H 5 OH in aqueous-based electrolytes remains a significant challenge. In this paper, we report Cu octahedra modified with low-coordinated Cu nanoclusters (Cu oct @Cu_NCs) as an efficient electrocatalyst for CO 2 RR to C 2 H 5 OH. Notably, the defect-site-rich Cu nanoclusters can promote the adsorption of *CO and increase the *CO coverage on Cu octahedra enclosed by Cu(1 1 1), thus promoting CO 2 RR to C 2 H 5 OH. We achieved a high Faradaic efficiency (FE) of 48.16 % for C 2 H 5 OH, and that of the C 2+ products is 83.31 % at −1.17 V vs. RHE. This study provides a surface nanostructured route for rationalizing efficient and selective copper electrocatalysts for CO 2 RR.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2024
·
IF 14
Mingdong Sun,Wenwen Guan,Cailing Chen,Chao Wu,Xiaoling Liu,Biao Meng,Tao Chen,Yu Han,Jun Wang,Shibo Xi,Yu Zhou
The synergy of single atoms (SAs) and nanoparticles (NPs) has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction (CO 2 RR); however, the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design. Herein, a Ni 2+ -loaded porous poly(ionic liquids) (PIL) precursor synthesized through the free radical self-polymerization of the ionic liquid monomer, 1-allyl-3-vinylimidazolium chloride, was pyrolyzed to prepare the Ni, N co-doped carbon materials, in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature. The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO 2 into CO. Operando Ni K -edge X-ray absorption near-edge structure (XANES) spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs. The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites. In the electroreduction of CO 2 , the co-existence of Ni SAs and NPs strengthened the CO 2 activation and the affinity towards the key intermediate of *COOH, lowering the free energy for the potential-determining *CO 2 → *COOH step, and therefore promoted the catalysis efficiency.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）