ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Xiafei Gao,Heng Yang,Jianghui Qiu,Limin Liu,Juan Peng
The oxidation of aldehydes on a copper-based electrocatalyst within a small potential window can produce hydrogen at the anode, thus offering a bipolar hydrogen production system. However, the inherent activity and stability of Cu-based electrocatalysts for aldehyde oxidation are still not satisfactory in practical application. Herein, by coating an ultrathin carbon shell on the copper sphere, an effective and stable formaldehyde oxidation reaction (FOR) can be realized to produce H2 at a very low potential. FOR needs only a potential of 0.13 V (vs RHE) to reach a current density of 100 mA cm–2. By coupling FOR with hydrogen evolution reaction (HER), hydrogen is generated simultaneously at both the cathode and the anode. The Faraday efficiency of H2 at the bipolar state is close to 100%. In a flow cell, it needs a low cell voltage of 0.1 V to reach a current density of 100 mA cm–2. Moreover, it can be operated steadily for more than 30 h at high current density. The carbon shell acts as an armor to protect the Cu(0) sites, avoid the oxidation of copper, and keep the catalyst activity for a long time in the electrolytic process. Experimental and theoretical calculation results indicate that electron transfer occurs at the interface between the copper core and ultrathin carbon shell. The ultrathin carbon-coated Cu reduces the reaction energy barrier, making the C–H bond more easily fractured and facilitating H coupling to generate H2. This study provides a basic principle for the design of copper-based electrocatalysts with long durability and activity.
研究领域:
电化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Jing Wang,Bingxin Guo,Junting Sun,Yingshuang Zhou,Chengfei Zhao,Zhongzhe Wei,Junjie Guo
The design and construction of electrocatalysts with multiple components to modulate the intrinsic catalytic activity is a compelling strategy to achieve Pt-like activity for hydrogen generation. Challenging on the inert Cu-based electrocatalysts for water reduction, herein, a novel and fruitful CuRu-based electrocatalysts (RuCuO x /NC) is established by combining dual-templates assembling and pyrolysis protocol with a subsequent hot-alkali corrosion. Benefitting from the synergetic effect of Cu 2+1 O (with copper excess defects) and Ru, the as-prepared RuCuO x /NC affords brilliant activity and stability under alkaline condition. In 1 M KOH, the RuCuO x /NC provides Pt-like activity with overpotential of ∼29 mV to reach 10 mA cm −2 . Theoretical calculations certified that H 2 O dissociation was accelerated and hydrogen adsorption free energy was optimized by the cooperation of Cu 2+1 O and Ru. This work proposes a promising methodology to construct multi-components electrocatalysts, which may lend perspective for the design of advanced electrocatalysts for renewable energy systems.
研究领域:
材料科学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2025
·
IF 2
Huilong Xu,Yi Xu,Qian Zhang,Qianli Zhang,Jie Liu,Haidong Bian
The methanol oxidation reaction (MOR) serves as a significant supplementary technique in the overall water splitting process and is recognized as a promising strategy for reducing the potential required to generate renewable hydrogen energy. This study presents the development of cost-effective and easily fabricated copper-based electrocatalysts through a straightforward anodization method. The resulting Cu-based electrocatalyst has been employed to evaluate the efficacy of the MOR in enhancing the water splitting process. Notably, the performance of the synthesized Cu2O/CuO electrocatalyst demonstrates a substantial improvement in the required overpotential, decreasing from 425 mV in 1.0 M KOH to 212 mV in 1.0 M KOH and 1.0 M methanol, to achieve a current density of 10 mA cm-2. The present work presents us a new way to reduce the necessary potential for the overall water splitting process using affordable Cu-based catalysts.
研究领域:
材料科学
·
能源科学
✓ 已验证
DOI
高影响因子
ACS Nano
·
2022
·
IF 18.027
Xiaohui Zhong,Shujie Liang,Tingting Yang,Gongchang Zeng,Zuqi Zhong,Hong Deng,Lei Zhang,Xueliang Sun
Using the electrochemical CO2 reduction reaction (CO2RR) with Cu-based electrocatalysts to achieve carbon-neutral cycles remains a significant challenge because of its low selectivity and poor stability. Modulating the surface electron distribution by defects engineering or doping can effectively improve CO2RR performance. Herein, we synthesize the electrocatalyst of Vo-CuO(Sn) nanosheets containing oxygen vacancies and Sn dopants for application in CO2RR-to-CO. Density functional theory calculations confirm that the incorporation of oxygen vacancies and Sn atoms substantially reduces the energy barrier for *COOH and *CO intermediate formation, which results in the high efficiency, low overpotential, and superior stability of the CO2RR to CO conversion. This electrocatalyst possesses a high Faraday efficiency (FE) of 99.9% for CO at a low overpotential of 420 mV and a partial current density of up to 35.22 mA cm–2 at −1.03 V versus reversible hydrogen electrode (RHE). The FECO of Vo-CuO(Sn) could retain over 95% within a wide potential area from −0.48 to −0.93 V versus RHE. Moreover, we obtain long-term stability for more than 180 h with only a slight decay in its activity. Therefore, this work provides an effective route for designing environmentally friendly electrocatalysts to improve the selectivity and stability of the CO2RR to CO conversion.
研究领域:
材料科学
·
环境科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2024
·
IF 14
Yinuo Wang,Yian Wang,Qinglan Zhao,Hongming Xu,Shangqian Zhu,Fei Yang,Ernest P. Delmo,Xiaoyi Qiu,Chi Song,Juhee Jang,Tiehuai Li,Ping Gao,M. Danny Gu,Minhua Shao
Urea generation through electrochemical CO 2 and NO 3 − co-reduction reaction (CO 2 NO 3 RR) is still limited by either the low selectivity or yield rate of urea. Herein, we report copper carbonate hydroxide (Cu 2 (OH) 2 CO 3 ) as an efficient CO 2 NO 3 RR electrocatalyst with an impressive urea Faradaic efficiency of 45.2% ± 2.1% and a high yield rate of 1564.5 ± 145.2 μg h −1 mg cat −1 . More importantly, H 2 evolution is fully inhibited on this electrocatalyst over a wide potential range between −0.3 and −0.8 V versus reversible hydrogen electrode. Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu 2 (OH) 2 CO 3 by combining the two intermediates, *COOH and *NHO. This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO 2 NO 3 RR, and provide guidance for rational design of more advanced catalysts.
研究领域:
电化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2024
·
IF 7.2
Shikai Liu,Chuqiao Shi,Chaokai Xu,Haichuan Zhang,Wenqi Li,Valentín Briega-Martos,Qian He,Yimo Han,Yao Yang
CO2 reduction reaction (CO2RR) facilitates the sustainable synthesis of fuels and chemicals. Although copper (Cu) enables CO2-to-multicarbon product (C2+) conversion, Cu-based electrocatalysts, particularly nanocatalysts, face challenges in poor selectivity and stability owing to the highly dynamic nature of Cu atoms under reaction conditions. Core–shell structures present a promising approach to address these issues by modulating the Cu overlayer–substrate interactions with atomic-level precision. Here, we report on Pd@Cu core–shell structures with atomically thin and nanometer-thick Cu overlayers on single-crystal Pd nanocubes with {100} facets promoting the CO2-to-C2+ conversion. The microstructures and surface compositions at the atomically sharp Pd/Cu interface were investigated by atomic-scale scanning transmission electron microscopy (STEM) imaging and electron energy-loss spectroscopy (EELS). Our results reveal that atomic-layer Cu epitaxially grows on Pd and adapts to the lattice of the Pd substrate. The reaction-driven migration of atomic-layer Cu is effectively suppressed on Pd due to the strong Cu–Pd interaction. While Pd only reduces CO2 to C1 products, atomic-layer Cu on Pd can initiate the C2+ production during the CO2RR. Thick Cu overlayers (∼15 nm) on Pd further enhance the C2+ faradaic efficiency while undergoing significant structural reconstruction, with only the 2–3 nm Cu layers near the Pd surface remaining stable and resistant to Cu migration after the CO2RR. We anticipate that Pd@Cu core–shell structures with intermediate Cu shell thickness hold significant potential for enhancing C2+ selectivity while maintaining high stability of nanocatalysts for CO2 reduction to liquid fuels.
研究领域:
材料科学
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化学工程
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Xiaofan Yang,Siyu Yi,Zhaolong Wang,Zhongqiu Wu,Ying Zhang,Junjie Yuan,Haibo Wang,Xiaojie She,Hui Xu
Electrocatalytic CO2 Reduction Reaction (ECO2RR) driven by renewable energy, which could convert CO2 into fuels or value-added chemicals, has become an effective approach to address environmental issues and the energy crisis. However, due to the low selectivity, the inferior activity, and unmanageable reconstruction of catalysts, the path of ECO2RR remains a significant challenge. In this study, a series of electrocatalysts composed of copper–lanthanum nanoparticles dispersed within a nitrogen-doped carbon framework (LaCu@NCF-x, where x represents the abbreviation of calcination temperatures) were synthesized by calcining the mixture of polymers and metal ions, in which thermal control is the key to the catalyst preparation process. Phase and morphological characterizations reveal that the degree of carbonization and the accessibility of active sites were modulated by the temperature of calcination. The study highlights the importance of the synergistic and confinement effects of the encapsulating carbon layer, which not only provides a favorable matrix for the nanoparticles but also mitigates the reconstruction of electrocatalysts, thereby significantly enhancing its performance in CH4 production during ECO2RR. In particular, the LaCu@NCF-3 catalyst demonstrates the maximum Faraday efficiency (FE) of CH4 up to 64.6% at −1.177 V vs RHE and superior stability. Moreover, it also maintains a high selectivity (FECH4 ≥ 60%) over the wide potential range from −0.977 V to −1.577 V vs RHE. This study provides a novel approach to the fabrication of efficient and stable Cu-based electrocatalyst for ECO2RR to CH4.
研究领域:
材料科学
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环境科学
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能源研究
✓ 已验证
产品关联
DOI
高影响因子
Advanced Energy Materials
·
2019
·Vol. 9
·期 27
·1901396
·
IF 24.884
Hao Yang,Yu-wen Hu,Jun-jie Chen,M.-Sadeeq (Jie Tang) Balogun,Ping-ping Fang,Shanqing Zhang,Jian Chen,Yexiang Tong
The challenge in the artificial CO 2 reduction to fuel is achieving high selective electrocatalysts. Here, a highly selective Cu 2 O/CuO heterostructure electrocatalyst is developed for CO 2 electroreduction. The Cu 2 O/CuO nanowires modified by Ni nanoparticles exhibit superior catalytic performance with high faradic efficiency (95% for CO). Theoretical and experimental analyses show that the hybridization of Cu 2 O/CuO nanowires and Ni nanoparticles can not only adjust the d-band center of electrocatalysts to enhance the intrinsic catalytic activity but also improve the adsorption of COOH* intermediates and suppress the hydrogen evolution reaction to promote the CO conversion efficiency during CO 2 reduction reaction. An in situ Raman spectroscopic study further confirms the existence of COOH* species and the engineering intermediates adsorption. This work offers new insights for facile designing of nonprecious transition metal compound heterostructure for CO 2 reduction reaction through adjusting the reaction pathway.
研究领域:
材料科学
·
电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2022
·Vol. 39
·期 2
·246-252
·
IF 2.726
Wang Renquan,Li Tiantian,Gao Rui,Qin Jiaqi,Li Mengyao,Guo Yizheng,Song Yujiang
With the excessive consumption of fossil fuels and the massive emission of CO 2 , it has led to a series of environmental crises posing a serious threat to sustainable development. Electrochemical CO 2 reduction reaction (CO 2 RR) to ethylene helps solve these serious environmental crises. Herein, we report the synthesis of a copper-based electrocatalyst by pyrolysis of yolk-shell structured HKUST-1 with partial substitution of trimesic acid by benzimidazole(nitrogen source). The electrocatalyst exhibits an ethylene Faradic efficiency(FE) of 25.8% and a partial ethylene current density of 23.7 mA/cm 2 , in addition, the electrocatalyst can maintain stable performance during 10 h of electrolysis, which are all better than those of the electrocatalyst without nitrogen dopant. According to electrochemical measurements and X-ray photoelectron spectroscopy(XPS), we propose that the nitrogen dopant plays an effective role in stabilizing Cu(I) species and promoting CO 2 molecules activation, as well as suppressing the reduction of Cu(I) species during electrolysis. Eventually, the performance of the electrocatalyst toward CO 2 RR is studied in a flow cell. This work provides a new route for the design of Cu-based electrocatalyst toward electrochemical CO 2 conversion into ethylene.
研究领域:
材料科学
·
电化学
·
环境科学
·
可持续能源
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Xuran Mao,Yanbing Huang,Yue Xiao,Xun Liu,Yan Pei,Qianwen Chen,Xiruo Wang,Wen Guo,Hongbing Yang,Fuxi Bao
Developing highly efficient and robust electrocatalysts to enhance the kinetics of electrochemical nitrate reduction reaction (NO 3 RR) to ammonia is crucial for realizing the conversion and storage of green electrochemical ammonia energy. Herein, we constructed a molybdenum-doped metallic copper electrocatalyst (Cu-Mo 0.2 /NF) and systematically investigated the pivotal role of molybdenum dynamic recombination in enhancing the kinetics of the NO 3 RR. In situ Raman spectroscopy, XPS and ICP-OES reveals that Mo dissolves during the NO 3 RR process and recombines into Mo 2 O 7 2- species, which are adsorbed onto the surface of the electrocatalyst. The experimental results combined with DFT calculations indicates that this dynamic dissolution, reorganization, and adsorption process of Mo significantly activates *NO 3 , thereby greatly enhancing the kinetics of *NO 3 reduction to *NO 2 . Furthermore, Differential electrochemical mass spectrometry (DEMS) and in situ attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) elucidate the NO 3 RR pathway: *NO 3 → *NO 2 → *NO → *NOH → *N → *NH → *NH 2 → *NH 3 . This reaction mechanism, which circumvents high-energy-barrier step (NO → N 2 O), endows the electrocatalyst with superior kinetics and high selectivity. Benefiting from the dynamic dissolution and redeposition of Mo and the advantages of the reaction pathway, the electrocatalyst achieves a record ammonia yield ( 1.55 mmol h −1 cm −2 ) with near-unity Faradaic efficiency ( 98.99 % ), and 30 h stability.
研究领域:
电催化
·
能源化学
·
材料科学
·
环境修复
·
可持续能源
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Tinghui An,Nan Wang,Jiaqi Li,Yuhao Wang,Zongxuan Bai,Dong Xiang,Kedi Cai
Cu-based electrocatalysts possesses superior potential to produce energy-dense fuels and value-added chemicals in electrocatalytic CO 2 reduction reaction (eCO 2 RR). Nevertheless, the desperately desired target C 2 selectivity is fundamentally constrained by inevitable hydrogen evolution reaction (HER), C 1 products competition and sluggish reaction kinetics, especially for ethanol. Herein, the strategy of introducing Mg on CuO is proposed to aim at modulating adsorption energetics of oxygen-associated active species, which can effectively suppress competing pathways while boosting ethanol production. Benefitting from the modified electronic structure and lattice compressive strain induced by Mg-doping, Mg 0.34 @CuO exhibited 77.5 % of C 2 FE with remarkable stability, in which FE C2H5OH could reach 48.5 % with total current density of 245.5 mA cm −2 . Density functional theory (DFT) calculation revealed that Mg-doped Cu surface exhibits multiple catalytic function, such as suppressed HER, increased surface CO coverage and accelerated H 2 O dissociation, which can be conducive to promote ethanol production. Incorporation of Mg significantly reduces the energy barrier for asymmetric CO-CHO coupling reaction and stabilizes C-O bond in *CH 2 CHO intermediate (shared by ethylene (C 2 H 4 ) and ethanol (C 2 H 5 OH)) by enhancing d-p orbital coupling, thus prioritizing C 2 H 5 OH pathway. Furthermore, it could achieve a high discharge capacity of 14944 mAh g −1 and stable charge-discharge operation of 153 cycles in Li-CO 2 batteries that utilize Mg 0.34 @CuO as cathode material. This work demonstrates a generalizable approach to regulate eCO 2 RR activity and selectivity, and meanwhile shows great application potential in rechargeable Li-CO 2 batteries.
研究领域:
电化学
·
能量转换
·
材料科学
·
催化
·
环境科学
·
理论化学
✓ 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）