ACS Sustainable Chemistry & Engineering
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2024
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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
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环境科学
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电化学
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DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2020
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IF 9.038
Y.L. Zhao,G.G. Li,H.M. Hou,J.C. Shi,S.N. Luo
We investigate atomic and molecular emission of laser-ablated nitromethane in an Ar or N 2 buffer gas, with fs laser-induced breakdown spectroscopy. The electronic bands of CN, C 2 , and NH molecules and the atomic transition lines of C I, N I, and H α are identified. The time series of the emissions are obtained, and the formation mechanisms of CN and C 2 are deduced. The CN violet system, the B 2 Σ + -X 2 Σ + (0-0) band, is chosen to extract plasma temperature from the experimental spectra.
研究领域:
物理化学
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光谱学
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产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 25
·15082-15089
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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
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电化学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
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2022
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IF 7.392
Fangfang Chang,Juncai Wei,Yongpeng Liu,Wenwen Wang,Lin Yang,Zhengyu Bai
Converting CO 2 to value-added chemicals and fuels by the electrocatalytic reduction reaction (CO 2 RR) is a promising strategy for reducing CO 2 emissions and achieving clean energy storage. Herein, Cu 2 O catalysts with various morphologies (hexapod concave rhombic dodecahedrons microcrystals enclosed with (3 3 1), (1 1 1) and (1 0 0) facets (D-Cu 2 O), cubic microcrystals enclosed with (1 0 0) facet (C-Cu 2 O) and octahedron microcrystals with (1 1 1) and (1 0 0) facets (O-Cu 2 O)) are prepared via the wet chemical reduction method. The in-situ formation of D-Cu 2 O/Cu, C-Cu 2 O/Cu and O-Cu 2 O/Cu surface/interface and the conversion mechanism of CO 2 to C 2+ products have been systematically studied. The electrocatalytic performance of D-Cu 2 O/Cu for CO 2 to form C 2+ products is superior to that of C-Cu 2 O/Cu and O-Cu 2 O/Cu, which the Faraday efficiencies (FE) of C 2+ products (ethylene and ethanol) reaches 70 %. The experimental results combined in-situ Raman spectroscopy and density function theory (DFT) calculations demonstrate that the good electrochemical performance is relate to the surface reconstruction and facet interface, which provides a positive local electronic environment to enhance the adsorption of *CO intermediates and reduces the energy barrier for the activation the C C coupling. This study will provide a new approach to improve the selectivity of CO 2 RR by interface engineering and surface.
研究领域:
材料科学
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电化学
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理论计算
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Jiacheng Sun,Xinyu Yu,Jiahe Li,Zhenglian Xue,Kai Liu,Chong Zhang
Nature-inspired protein materials boast superior mechanical and biological properties, but efficient and sustainable production remains a challenge. Here, we present a microbial secretion platform in Corynebacterium glutamicum for the production of supercharged polypeptides (SUPs) using C2 feedstock as the primary carbon source, featuring a simplified purification process for the development of functional protein materials. SUPs with the Val-Pro-Gly-Lys-Gly (VPGKG)ₙ motif were successfully transported extracellularly via the Sec-dependent pathway; however, increasing the number of repeat units resulted in expression instability and truncation. Optimized codon designs with reduced unit sequence homology, significantly stabilizing expression and enabling efficient secretion of SUP K72 (VPGVG(VPGKG)₉)₈. Through comparative analyses of host strains, promoters, and carbon sources, we identified the ATCC13032/A256/Acetate (3 A system) as the optimal platform for large-scale K72 production. This system, specifically activated during the glyoxylate cycle under acetate metabolism, achieved K72 secretion levels that were twice of the traditional P tac /IPTG system. Following systematic optimization of bioprocess parameters, including medium composition and fermentation conditions, production was successfully scaled up to a 5-L bioreactor, achieving a final titer of 3.67 g/L—far surpassing the previously reported 0.2–0.5 g/L in Escherichia coli using a 100-L fermenter. After chromatography-free purification, K72 was fabricated into high-strength protein fibers with an ultimate tensile strength of 308.97 ± 43.76 MPa. Additionally, an ultra-strong bio-glue was developed, achieving a fracture strength of 14.08 ± 1.26 MPa on hard substrates. This study demonstrates a sustainable approach for producing proteins from C2 feedstock, providing a cost-effective solution to advance the commercialization of protein-based materials.
研究领域:
生物技术
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合成生物学
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蛋白质工程
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发酵工程
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产品关联
DOI
高影响因子
ChemCatChem
·
2025
·
IF 3.9
Yuwen Wang,Xuan Zhang,Yajuan Wei,Jingbo Zhang
Cu-based tandem catalysts have been widely studied due to their excellent performance in electrocatalytic reduction of carbon dioxide (CO2RR) to produce C2+ products. However, during the CO2RR process, Cu atoms face the issue of dynamic restructuring, resulting in relatively poor stability and single-product selectivity. Herein, Cobalt phthalocyanine (CoPc) was integrated with Cu nanoparticles (NPs) to prepare a tandem catalyst (Cu/CoPcx) by in-situ growth method, significantly enhancing the selectivity of Cu-based catalysts for C2+ products. The optimal material, Cu/CoPc0.004, achieved a Faradaic efficiency (FE) of 73.17% for C2+ products, with a C2+ product current density exceeding 377 mA/cm2. More importantly, tandem catalyst Cu/CoPc0.004 exhibits high selectivity for ethylene, achieving a FE of 52.35% at -1.26 V (versus reversible hydrogen electrode) with a high ethylene current density (270 mA/cm2). The experimental results indicate that the interaction between CoPc and Cu NPs introduces numerous oxygen vacancies and stabilizes the presence of Cu+. Moreover, the unique structure of the cascade catalyst enables CoPc to provide a large amount of CO intermediates for Cu active sites, thus promoting C-C coupling and facilitating the formation of C2+ products.
研究领域:
材料科学
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电化学
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催化反应
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Tete Zhao,Xupeng Zong,Jiuding Liu,Jialei Chen,Keqiang Xu,Xiao Wang,Xijie Chen,Wutong Yang,Fangming Liu,Meng Yu,Fangyi Cheng
Copper-based nanomaterials are attractive in CO 2 electroreduction into valuable chemicals but still suffer from limited selectivity of C 2+ products due to the parasitic hydrogen evolution reaction and inefficient dimerization of absorbed CO intermediate (*CO). Herein, we report an in situ polymerization strategy to coat hydrophobic polymer containing methoxyl silane ((CH 3 O) 3 Si–) and trifluoromethyl (–CF 3 ) functional groups on Cu nanoparticles. The optimized Cu-poly exhibits a high Faradaic efficiency of 71.08 % and a remarkable partial current density of 355.4 mA cm −2 for C 2+ products in a membrane electrode assembly electrolyzer using a bicarbonate electrolyte. A combined study of density functional theory calculations and in situ infrared characterizations indicates that the enhanced performances could be ascribed to the decreased formation energy of *COCOH, induced by the withdraw-electron effect of –CF 3 and enhanced coverage of *CO. This work offers a new insight in tuning the electrocatalytic microenvironment through the surface polymerization process.
研究领域:
材料科学
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电化学
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环境科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Bing Chang,Fengtao Zhang,Zhaojun Min,Nan Wang,Qingchun Xia,Jing Fan,Maohong Fan,Jianji Wang
Cu-based catalysts, especially co-sites of Cu 0 and Cu Ⅰ , are the best competitors for electrochemical CO 2 fixation to produce multi-carbon (C2 + ) products. However, it is challenging to construct highly stable Cu Ⅰ sites due to the changeability of its valence state and electronic structure in the electroreduction process, and the mechanism is also elusive. Herein, a 2D conductive Cu Ⅱ -MOF film (Cu Ⅱ HHTP@Cu 0 ) is prepared on Cu (1 0 0) foil by in-situ electrochemical assembly. After pre-reduction, the in-situ produced Cu 2 O clusters are confined in the cavities of the film created by the local breaking of the MOF framework to construct a unique Cu Ⅰ -Cu Ⅱ HHTP@Cu 0 catalyst, so that a novel strategy is proposed to stablize highly dispersed Cu Ⅰ sites during electrochemical reduction, thus protecting the Cu 2 O clusters from further reduction and ensuring the coexistence of Cu Ⅰ (1 1 1)-Cu 0 (1 0 0) sites. As such, the current density of CO 2 electrochemical reduction catalyzed by this catalyst exceeds 300 mA cm −2 , the duration overs 50 h, and the C2 selectivity achieves 72.6 %. In-situ spectroscopy and theoretical calculations reveal that the optimized microenvironment of the Cu Ⅰ (1 1 1) sites reduces the energy barrier of *OCCOH coupling, and Cu 0 (1 0 0) sites increase the coverage of *CO, thus boosting the production of C2 products.
研究领域:
材料科学
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电化学
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产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Yanru Zhu,Zhijun Zhang,Jian Zhang,Shuangjiang Jiang,Zhe An,Hongyan Song,Xin Shu,Wei Xi,Lirong Zheng,Jing He
ABSTRACT Photosynthesis is a potential strategy to enable endergonic process that usually needs high-temperature in thermochemistry to supply the energy for inert-bond activation and/or strong endothermic reaction . The conversion of CO 2 into value-added C 2 -oxygenates is a promising process to realize artificial photosynthesis , but suffers from relatively lower efficiency due to complex multi-electron (≥ 10) transfer processes and sluggish kinetics of C–C coupling. This work proposes an all-new H 2 O-promoted strategy for efficient production of C 2 oxygenates from the concurrent activation and subsequent co-conversion of CO 2 with CH 4 under photo-thermal cooperation, in which photocatalytic H 2 O-splitting derived active hydrogen species for CO 2 activation, and concomitant active oxygen species for CH 4 activation. A formation rate of as high as 2.05 mmol g −1 h −1 for C 2 -oxygenates (CH 3 CHO and CH 3 CH 2 OH) in a selectivity of > 86% has been afforded over SrTiO x supported CuCo under 200 °C and ultraviolet-visible illumination. It has been revealed that SrTiO x drives photocatalytic H 2 O-splitting under the excitation primary from ultraviolet light, paired Cu I /Cu 0 sites promote the formation of *CH x O intermediate from CO 2 , Co sites conduct CH 4 -to-*CH 3 , and C–C coupling of *CH x O and *CH 3 on adjacent Cu-Co facilitates the generation of C 2 -oxygenates.
研究领域:
化学工程
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催化科学
·
能源转换
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产品关联
DOI
高影响因子
ChemistryOpen
·
2021
·Vol. 10
·期 5
·560-566
·
IF 2.911
Yingshuang Hui,Yulu Zhan,Wenrong Hou,Lou Gao,Yahong Zhang,Yi Tang
Graphical The product control of C6 aldose toward C6, C4 and C2 alditols have been achieved, which have depended on the well-matched between retro-aldol condensation and hydrogenation process driving by temperature, H 2 pressure and injection modes. Alcohols have a wide range of applicability, and their functions vary with the carbon numbers. C6 and C4 alditols are alternative of sweetener, as well as significant pharmaceutical and chemical intermediates, which are mainly obtained through the fermentation of microorganism currently. Similarly, as a bulk chemical, C2 alditol plays a decisive role in chemical synthesis. However, among them, few works have been focused on the chemical production of C4 alditol yet due to its difficult accumulation. In this paper, under a static and semi-flowing procedure, we have achieved the product control during the conversion of C6 aldose toward C6 alditol, C4 alditol and C2 alditol, respectively. About C4 alditol yield of 20 % and C4 plus C6 alditols yield of 60 % are acquired in the one-pot conversion via a cascade retro-aldol condensation and hydrogenation process. Furthermore, in the semi-flowing condition, the yield of ethylene glycol is up to 73 % thanks to its low instantaneous concentration.
研究领域:
生物化学
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有机化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2014
·Vol. 90
·期 3
·415-422
·
IF 2.494
Yanping Chen,Yiming Xu,Dang-guo Cheng,Yingcai Chen,Fengqiu Chen,Xiaoyong Lu,Yiping Huang,Songbo Ni
BACKGROUND The synthesis of C 2 –C 4 hydrocarbons from coal or biomass-derived syngas has received increasing attention because of the resource constraints of petroleum. The present study explores direct production of hydrocarbons from syngas over bifunctional catalyst containing methanol synthesis catalyst CuO–ZnO–Al 2 O 3 (CZA) and SAPO-34 zeolite. RESULTS The synthesis of C 2 –C 4 hydrocarbons from syngas was investigated over CZA/SAPO-34 bifunctional catalyst at temperatures ranging from 240 to 440°C. The results indicate that higher temperatures aggregate Cu metal and lead to the deactivation of CZA. The predominant products are dimethyl ether (DME) and methanol at temperatures from 280 to 360°C and a small amount of hydrocarbons are found due to the deactivation of SAPO-34 caused by a type of coke named ‘inert coke’. While 96.5% selectivity of C 2 –C 4 hydrocarbons in products of all hydrocarbons can be obtained at 400°C with less coke named ‘active coke’. CONCLUSION Reaction temperatures have significant effect on the selectivity of C 2 –C 4 hydrocarbons and coke species of SAPO-34. The ‘active coke’ of poly methyl-substituted benzene/naphthalene (MB/MN) acts both as an intermediate and as coke deposition. The ‘inert coke’ of poly methyl-substituted adamantine (MA) and other groups-substituted benzene/naphthalene acts only as coke depositions. Comprehensive consideration of the characteristics of this bifunctional catalyst, shows that a moderate temperature for C 2 –C 4 hydrocarbons synthesis from syngas might be approximately 400°C. © 2014 Society of Chemical Industry
研究领域:
化学工程
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催化化学
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产品关联
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
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