Small
·
2024
·
IF 13
Yi-Ran Du,Xiao-Qiang Li,Xian-Xia Yang,Guo-Yi Duan,Yong-Mei Chen,Bao-Hua Xu
In this study, the copper-nickel (Cu–Ni) bimetallic electrocatalysts for electrochemical CO 2 reduction reaction(CO 2 RR) are fabricated by taking the finely designed poly(ionic liquids) (PIL) containing abundant Salen and imidazolium chelating sites as the surficial layer, wherein Cu–Ni, PIL–Cu and PIL–Ni interaction can be readily regulated by different synthetic scheme. As a proof of concept, Cu@Salen-PIL@Ni(NO 3 ) 2 and Cu@Salen-PIL(Ni) hybrids differ significantly in the types and distribution of Ni species and Cu species at the surface, thereby delivering distinct Cu–Ni cooperation fashion for the CO 2 RR. Remarkably, Cu@Salen-PIL@Ni(NO 3 ) 2 provides a C2+ faradaic efficiency (FE C2+ ) of 80.9% with partial current density ( j C 2+ ) of 262.9 mA cm −2 at −0.80 V (versus reversible hydrogen electrode, RHE) in 1 m KOH in a flow cell, while Cu@Salen-PIL(Ni) delivers the optimal FE C2+ of 63.8% at j C2+ of 146.7 mA cm −2 at −0.78 V. Mechanistic studies indicates that the presence of Cu–Ni interfaces in Cu@Salen-PIL@Ni(NO 3 ) 2 accounts for the preserve of high-valence Cu(I) species under CO 2 RR conditions. It results in a high activity of both CO 2 -to-CO conversion and C–C coupling while inhibition of the competitive HER.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 25
·15082-15089
·
IF 10.7
Zongmiao Li,Zhu Liu,Shiju Li,Yuhou Pei,Di Li,Jiale Mao,Rong Zhou,Chuntian Qiu,Yingying Lu,Bing Zhang
Electrochemical conversion of carbon dioxide (CO2RR) into high-value multi-carbon (C2+) chemicals and fuels is of great significance for carbon neutrality, and so far Cu-based materials are still the dominant electrocatalysts with practical application potential for C2+ products during the CO2RR. However, Cu-based catalysts usually face problems such as an unstable valence state and lattice structure, low efficiency, and a narrow potential window for C2+ products which affect the comprehensive performance of the catalysts. Herein, we develop a simple co-precipitation-hydrothermal method for introducing zirconium dioxide (ZrO2) into copper oxide (CuO) to improve the selectivity of C2+ products via in situ reconstruction. The optimized CuO–ZrO2-1.0 catalyst exhibits a high faradaic efficiency of 82.3% for C2+ products with an industrial partial current density over 200 mA cm−2, which presents a more than 1.7-fold improvement compared to that of CuO, also exceeding that of lots of Cu-based catalysts previously reported. DFT and in situ characterization studies reveal that the introduction of ZrO2 can induce the electronic distribution and stabilize the Cu+ species during the in situ reconstruction process which contributes to moderate adsorption and enhanced coupling of *CO intermediates to obtain C2+ products.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Rui Yang,Zipeng Zeng,Zhen Peng,Jiafang Xie,Yiyin Huang,Yaobing Wang
Currently most of research efforts for selective electrocatalysis CO 2 reduction to C2+ products have relied on crystalline Cu-based catalysts; amorphous Cu with abundant low-coordinated atoms holds greater promise for this conversion yet remains relatively underexplored. Here we report an amorphous urchin-like Cu@nanosilica hybrid synthesized by electrostatic coupling Si polyanions with Cu salt in hydrothermal processes. The Cu@nanosilica electrocatalyst displays excellent CO 2 electroreduction activity and selectivity with a Faradic efficiency of 70.5% for C2+ product production, and higher stability compared to the crystalline Cu counterpart. The solar-driven CO 2 electrolysis yields an energy efficiency of 20% for C2+ product production. Mechanism study reveals that the urchin-like Cu@nanosilica catalyst with amorphous Cu/Cu + dispersion enhances CO 2 adsorption and activation to facilitate generation of CO 2 − * and possible CO* intermediates, and suppresses hydrogen evolution concurrently. The combined effects of both aspects promote efficient C2+ product production from CO 2 electroreduction.
研究领域:
材料科学
·
电化学
·
能源转换
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Anbang He,Yong Yang,Qiang Zhang,Ming Yang,Qian Zou,Jun Du,Changyuan Tao,Zuohua Liu
Electrochemical reduction of CO 2 to C2 products on Cu-based catalysts provides a promising approach for controlling the global carbon balance and restoring renewable surplus electricity. The enhanced CO 2 adsorption and CO local concentration are beneficial for CO 2 conversion and C2 intermediates formation, promoting the progress of CO 2 utilization. Here, we report a bimetallic MOF-derived Co 3 O 4 -CuO x /C (M-CuCo/C) catalyst constructed with Co 3 O 4 and CuO x sites wrapped in the carbon skeleton, achieving efficient CO 2 activation and C2 generation under low overpotential. The optimized M-CuCo/C catalyst (Cu/Co ratio of 1:2) exhibits a total current density of 19.28 mA/cm 2 at −1.05 (V vs. RHE), which is 8.60 times than that on MOF-derived CuO x /C (M-Cu/C). The highest C2 faradic efficiency (FE) reaches 79.2% (-0.75 V vs. RHE), accompany with a C2 production rate of 275.6 μmol/(g·h). The special nanorods-like morphology assembled by dual sites significantly increases electrochemical surface area and electron transmission rate during eCO 2 RR. The local CO intermediates under real-time electrochemical environment are monitored via rotation ring disk electrode (RRDE) techniques. Combined with in situ infrared measurements and DFT studies, it’s demonstrated that CO 2 could be efficiently converted to CO under low overpotential on Co 3 O 4 sites, forming local CO-enriched environment around neighboring CuO x sites and further accelerating the process of C2 formation.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2020
·Vol. 32
·期 39
·2002382
·
IF 27.398
Changming Zhao,Gan Luo,Xiaokang Liu,Wei Zhang,Zhijun Li,Qian Xu,Qinghua Zhang,Huijuan Wang,Deming Li,Fangyao Zhou,Yunteng Qu,Xiao Han,Zezhou Zhu,Geng Wu,Jing Wang,Junfa Zhu,Tao Yao,Yafei Li,Henny J.M. Bouwmeester,Yuen Wu
Electrochemical reduction of CO to value-added products holds promise for storage of energy from renewable sources. Copper can convert CO into multi-carbon (C 2+ ) products during CO electroreduction. However, developing a Cu electrocatalyst with a high selectivity for CO reduction and desirable production rates for C 2+ products remains challenging. Herein, highly lattice-disordered Cu 3 N with abundant twin structures as a precursor electrocatalyst is examined for CO reduction. Through in situ activation during the CO reduction reaction (CORR) and concomitant release of nitrogen, the obtained metallic Cu° catalyst particles inherit the lattice dislocations present in the parent Cu 3 N lattice. The de-nitrified catalyst delivers an unprecedented C 2+ Faradaic efficiency of over 90% at a current density of 727 mA cm −2 in a flow cell system. Using a membrane electrode assembly (MEA) electrolyzer with a solid-state electrolyte (SSE), a 17.4 vol% ethylene stream and liquid streams with concentration of 1.45 m and 230 × 10 −3 m C 2+ products at the outlet of the cathode and SSE-containment layer are obtained.
研究领域:
材料科学
·
电化学
·
能源存储与转化
✓ 已验证
产品关联
DOI
PubMed
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
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Quhan Chen,Xiang Luo,Guohao Mu,Xinyi Mao,Hongfeng Yin,Edward Henry Lester,Tao Wu
Electrochemical reduction of CO2 to valuable C2+ chemicals using renewable energy is a crucial pathway for sustainable development, replacing traditional nonrenewable feedstocks. In this study, CuO-based materials were synthesized with and without microwave heating as electrocatalysts for CO2 reduction. The CuO synthesized under microwave irradiation (MW-CuO) showed a similar morphology to the conventionally heated samples but exhibited a higher density of defect sites with increased grain boundaries (GBs). MW-CuO electrodes with a Cu2+ and CO32– reactant ratio of 1.1 showed superior catalytic performance under identical reaction conditions. In particular, the catalytic activity of the MW-CuO electrode at −1.04 V vs RHE for the C2+ products is 49.3% higher than that of the CuO electrode. A faradaic efficiency (FE) of 71.9% is achieved for C2+ products, which is among the highest yields reported for OD-Cu catalysts. The spent MW-CuO electrode exhibited a significantly higher Cu+ to Cu0 ratio compared to the CuO electrode. The synergy of Cu(I) species and defective surface features is speculated to be responsible for the improved CO2ER selectivity toward multicarbon products. However, the activity decreased for longer reactions, which was attributed to the loss of defect sites and Cu agglomerations. This study highlights the effectiveness of a simple synthesis approach for the production of defect-rich electrocatalysts that improve the efficiency and selectivity of CO2 reduction.
研究领域:
材料科学
·
环境科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2022
·
IF 8.035
Lili Gao,Langlang Qin,Haonan Wu,Xuelian Li,Kai Qi,Qun Yi,Jiandong Zhang,Lijuan Shi
Electrochemical reduction of CO 2 (CO 2 ER) to high value-added multicarbon (C 2+ ) is a viable way to promote carbon–neutral cycle. To date, copper (Cu) is reported as the most effective metal catalyst toward C 2+ , but it remains a challenge to achieve high selectivity and large current density. Incorporating ionic liquid in Cu-based catalysis has been proved an effective strategy, however, most reported methods are either involved too much ionic liquid (IL) as electrolyte or too complex & unstable. Herein, an ionic liquid-embedded Cu electrocatalyst (Cu-IL/GDL) was innovatively constructed through one-step electro-codeposition method, in which a kind of amino-ionic liquid, AFIL, was anchored to the gas diffusion layer (GDL) and embedded by the deposited Cu. Under the excellent synergy between Cu and AFIL, Cu-IL/GDL exhibits higher faradaic efficiency toward ethylene (C 2 H 4, 40.67%) and C 2 (C 2 H 4 and C 2 H 5 OH, 61.39%) when directing CO 2 to carbon-fiber side of electrode in H-cell. To be precise, more Cu (1 0 0) facet is stabilized by the capping effect of AFIL, being in favor for C–C coupling; meanwhile more AFIL + is embedded by the deposited Cu, making for the initiation of CO 2 ER. Thus, this paper proposes a facial and effective strategy to reinforce Cu (1 0 0) facet, and couple and heighten the virtues of ionic liquid and Cu during CO 2 ER toward C 2 .
研究领域:
化学
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
ChemElectroChem
·
2021
·Vol. 8
·期 16
·3174-3180
·
IF 4.59
Yunxi Han,Shuaikang Zhu,Shuang Xu,Xiaopo Niu,Zhihong Xu,Rong Zhao,Qingfa Wang
Graphical The structural reconstruction of HKUST-1 on carbon fiber paper and the activity in CO 2 electroreduction is investigated. The HKUST-1 initially reconstructed into highly active 3D nanospheres and then into stable nanobelts after 120 minutes. The 3D nanospheres structure shows the best Faradaic efficiency of C 2 products up to 58.6 %. Metal-organic frameworks (MOFs) have been widely studied for electrochemical CO 2 reduction reaction (CO 2 RR). However, the application of negative potential tends to trigger its structural reconstruction and component alteration. It is of great significance to study the relationship between the structural evolution of MOF-derived materials and product selectivity under the reaction conditions. Herein, we fabricate a HKUST-1 thin film on carbon fiber paper by a facile electrodeposition approach to investigate the variation of CO 2 RR activity with HKUST-1 structural reconstruction. During the CO 2 RR process, the HKUST-1 reconstructs into two structures successively over time: 3D nanospheres composed of numerous small fragments and 3D nano-network composed of cross-linked nanobelts in different directions. The former shows a better catalytic activity due to more active sites, lower charge transfer resistance and higher Cu + /Cu 0 ratio. The optimum Faradaic efficiency (FE) of C 2 products (ethylene and ethanol) reaches 58.6 % at −0.98 V versus reversible hydrogen electrode (RHE).
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2021
·
IF 6.707
Hongyu Chen,Zhaojie Wang,Xiaofei Wei,Siyuan Liu,Peng Guo,Peng Han,Haowei Wang,Jinbao Zhang,Xiaoqing Lu,Baojun Wei
Electrochemical reduction of CO 2 to C 2+ products is a sustainable energy-driven pursuit for high added-value hydrocarbons. Tremendous efforts have been made to copper based electrocatalysts, which are well-known for producing C 2+ products. However, being short of well-defined catalysts with stable Cu δ+ electronic structure hinders its practical application and in-depth understanding. Herein, we developed a facile one-pot approach to prepare Cu δ+ -rich catalyst by doping phosphorus. Enhanced performance and tunable product selectivities are achieved due to the electron donor–acceptor interaction based on phosphorus content in series. C 2 hydrocarbons and alcohols are produced with high (~44.9%) selectivity, in which C 2 H 4 (30.7 ± 0.9%) is dominant at −1.6 V vs reversible hydrogen electrode (RHE). This P-Cu catalyst shows a significantly higher current density (57.2 mA cm −2 ) compared to pristine Cu. In addition, the favorable Cu δ+ is reserved during CO 2 RR contributing to a long-term stability. Experimental results and DFT calculations demonstrate that the Cu δ+ moiety facilitates the adsorption of carbon intermediates, C-C coupling and hence promotes the generation of C 2 H 4 energetically. The well-designed catalyst indicates the profit of electronic structure engineering in designing catalysts for multiple-step chemical conversions.
研究领域:
材料科学
·
催化化学
·
能源化学
✓ 已验证
DOI
高影响因子
Chem
·
2024
·
IF 19.1
Xi Cao,Shan Ren,Xue Zhang,Qikui Fan,Qingqing Chen,Jian Yang,Junjie Mao
Cu-based catalysts are boosting electrocatalysts in CO 2 reduction reactions to high-value multicarbon (C 2+ ) products. Because of the unstable Cu + species and the unclear microscopic structure in reactions, Cu-based catalysts still face significant challenges of low selectivity and poor durability at high current density. Herein, we report a thermodynamically driven comproportionation strategy for forming a Cu 0 /Cu + /Cu 0 interface to stabilize Cu + species. When tested in a flow cell containing neutral electrolyte, the sample showed a high C 2+ products Faradaic efficiency (FE C2+ ) of 92.3% at a partial current density of 276.9 mA cm −2 . In a membrane electrode assembly, the sample achieved a 90.1% FE C2+ and maintained continuous operation for over 50 h at industrial current density. Further investigation demonstrates outstanding FE C2+ of >80% at a large industrial current of 10 A. Mechanism studies reveal that the Cu 0 /Cu + /Cu 0 interface lowers the energy barrier for C–C coupling in the reaction, thus facilitating the conversion of CO 2 to C 2+ products.
研究领域:
电化学
·
催化材料科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Jiaqi Feng,Yanlin Wang,Guilin Li,Qizhou Xue,Min Wang,Xiaofu Sun,Shaojuan Zeng,Xiangping Zhang
Copper-based catalysts hold promise for electrochemical reduction of CO 2 to multi-carbon (C 2+ ) products, but achieving high selectivity and ampere-level current density remains challenging. A key hurdle lies in stabilizing Cu + species under reducing conditions, which are crucial for C-C coupling reaction. Herein, we modified Cu 2 O with sodium citrate through the coordination interaction between Cu atoms and carboxyl group. In situ spectroscopy analysis and theoretical studies revealed that the modification induced electron transfer from Cu 2 O to the citrate anion, stabilizing Cu + species under reduction conditions. Additionally, the presence of sodium citrate facilitated the hydrogenation of *CO to *CHO, with *CHO being more prone to C-C coupling reactions. Thereby, the as-prepared catalyst showed an C 2+ products Faradaic efficiency (FE) of 88.1 % at − 0.9 V vs reversible hydrogen electrode (RHE) with a C 2+ products partial current density ( j C2+ ) of 825.94 mA cm −2 and maintained over 80 % FE at − 1.1 V vs RHE with j C2+ of 1239.92 mA cm −2 . This work suggests that surface modification of Cu 2 O via carboxyl group is an effective strategy for altering the surface electronic structure of Cu 2 O and regulating the C-C coupling pathway, encouraging the exploration of more carboxyl-containing molecules for modifying copper-based catalysts to further enhance electrocatalytic performance.
研究领域:
电化学
·
催化材料
·
能源转换
✓ 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）