Chem
·
2024
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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
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Wei Zhou,Mazhar Ahmed Memon,Mengmeng Niu,Xinqiang Fan,Yanan Jiang,Xian Zhang,Yuan Liu
Copper (Cu) based catalysts are frequently used in CO 2 hydrogenation, particularly in reverse water-gas shift (rWGS) and CO 2 -to-methanol reaction. Cu 0 and Cu + are the key species affecting the catalyst performance and product distribution . Therefore, constructing and adjusting Cu 0 /Cu + active pairs is significant for the catalyst design . In this study, Cu 0 /Cu + active pairs are obtained by utilizing the properties of perovskite-type oxides (PTOs). A series of CaTi 1-x Cu x O 3 and Ca 0.8 La 0.2 Ti 1-x Cu x O 3 (x = 0.05, 0.10, 0.15, 0.30, 0.40 and 0.50) were synthesized via citric acid complexing method and part of the Cu species entered the PTOs lattice. After reduction, large Cu particles and highly-dispersed Cu clusters were obtained simultaneously. The dispersed Cu clusters have more interfaces with the PTOs and provide abundant Cu + while large Cu particles tend to aggregate and supply mainly Cu 0 . Cu 0 activates H 2 and CO 2 and plays a vital role in the rWGS reaction . Cu + is the active site for methanol synthesis and it can strongly absorb CO. The ratio of Cu 0 /Cu + varies with different Cu content and doping La can also adjust the chemical state of surface Cu. The performance test demonstrates that both excessively high and low Cu 0 /Cu + ratios are beneficial for CO generation, while a moderate ratio is suitable for methanol synthesis . These insights provide a method for regulating the chemical state of surface metal species and help the catalyst design for CO 2 hydrogenation.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
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2020
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IF 5.774
Bingqing Wang,Tao Fu,Baohua An,Yong Liu
Sulfate radicals-based advanced oxidation process (SRAOP) has received increasing attention in the wastewater treatment area because sulfate radicals have high redox potential. The key for SRAOP is to develop high efficient catalysts that can effectively and stably activate persulfate (PS) to produce sulfate radicals. Cu 2 O is a good activator of PS and photo-catalyst. However, its catalytic activity is relatively low because of the poor stability and the recombination of electron and holes. In theory, Cu 0 can reduce Cu 2+ to form Cu + , which can decrease the recombination of electron and holes from the Cu 2 O by the formation of heterojunction. In this study, Cu 0 -Cu 2 O was synthesized by a simple ball-milling method. The as-prepared Cu 0 -Cu 2 O was characterized and used to activate PS for sulfamerazine (SMZ) degradation by means of UV illumination. In the Cu 0 -Cu 2 O/PS/UV system, the removals of 100% SMZ and 30% TOC within 30 min were achieved, respectively, and the removal efficiency of SMZ decreased by only 12.2% after 5 cycles. The high efficiency and good catalytic stability of Cu 0 -Cu 2 O for the activation of PS were due to that Cu 0 and photo-induced electron of Cu 2 O promoted the conversion of Cu 2+ to Cu + . Quenching experiments demonstrated that the hydroxyl radicals and sulfate radicals contributed to SMZ degradation. However, the concentrations and fractions of radicals was affected by the initial pH of solution. Nine intermediate products were identified, and the degradation pathways were proposed, including the fission of sulfur and nitrogen bond, the oxidation of methyl group and the hydroxylation of benzene ring. The effects of initial pH, PS concentration, Cu 0 -Cu 2 O dosage and SMZ initial concentration on the degradation of SMZ were investigated. This study provided an effective catalyst that could simultaneously activate PS and utilize UV to form photo-induced electron, which could enhance the degradation and mineralization of organic pollutants.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
TETRAHEDRON
·
2023
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IF 2.1
Zhiwei Wang,Rong Zhao,Jia Lin,Chaoyang Liu,Qiang Jia,Changhu Chu
A highly efficient and Tempo-free catalytic aerobic alcohol oxidation method has been developed using charcoal-supported Cu 0 nanoparticles（Cu-A） in conjunction with pyridine. Various alcohols, bearing different functional groups, can be readily oxidized to their corresponding ketones and aldehydes under mild conditions.
研究领域:
化学
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催化
·
有机合成
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
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2022
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IF 9.794
Tong Dou,Jiawei Du,Jinqing He,Yiping Wang,Xuhui Zhao,Fazhi Zhang,Xiaodong Lei
The transformation of CO 2 into value-added products is a hot research topic. Metal copper as an electrochemical catalyst shows activity for generating multi-carbon products in CO 2 electroreduction. Herein, Cu 2 S nanorods/copper mesh (Cu 2 S/CM) is successfully fabricated, and exhibits high performance of CO 2 electroreduction to ethanol. At −0.8 V vs RHE , it achieved the Faraday efficiency (FE) of 13.5%, the partial current density of 13.3 mA cm −2 and the yield of 986.4 μmol L −1 h −1 for ethanol. Experiments and theoretical calculations indicated that the high performance is benefits from the high density of Cu 0 and Cu + pairs derived from Cu 2 S/CM during CO 2 electroreduction and an appropriate surface Cu 0 /Cu + ratio of 0.17. The Cu 0 –Cu + sites facilitate the adsorption of key intermediate *CH 2 CHO and decrease the energy barrier of the ethanol pathway. This work provides not only a new comprehension of CO 2 electroreduction with Cu 2 S catalyst but also a design idea based on Cu 0 –Cu + sites in Cu/Cu 2 S catalyst.
研究领域:
电化学
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催化
·
可再生能源
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2021
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IF 7.132
Tianhao Wang,Yi Zhao,Huiru Zhang,Weitian Hui
Carbon dioxide (CO 2 ) emissions from the combustion of fossil fuels cause the intensification of greenhouse effect. Consequently, a new non-noble nanoalloy of Ni 0 , Cu 0 and Fe 0 was prepared for the production of formate (HCO 2 − ) from CO 2 in flue gas by hydride transfer reaction under atmospheric pressure and mild temperature in this work. Under the optimal reaction conditions obtained by experimental optimization, which were that catalyst dosage was 1 g·L -1 , KBH 4 concentration was 0.15 mol·L -1 , reaction temperature was 55 °C, solution pH was 9.5 and flow velocity of flue gas was 0.5 L min -1 , the CO 2 conversion efficiency (CCE) was achieved as 55.97 %. Due to the employment of nanoalloy of Ni 0 , Cu 0 and Fe 0 , the CCE was improved by about 25 % compared with that in non-catalytic conditions, and meanwhile, the KBH 4 dosage was reduced by around 45 %. Based on the catalyst properties before and after the reaction as well as the product detection, we put forward that the electrode potential differences among the ternary transition metals resulted in the improvement of catalyst surface activity to promote KBH 4 activation and the hydride transfer reaction for CO 2 . The work presented herein is conducive to the development of novel transition metal-based nanomaterials for CO 2 resource utilization in a low-energy way.
研究领域:
环境科学
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Yingyu Ren,Yusen Yang,Lifang Chen,Lei Wang,Yawen Shi,Pan Yin,Wenlong Wang,Mingfei Shao,Xin Zhang,Min Wei
As a safe and environmentally friendly selective hydrogenation method, catalytic transfer hydrogenation (CTH) has aroused great interest in preparation of high-value-added products from biomass derived resources. Herein, a Cu-based catalyst (Cu/CuAl-MMO-400) was prepared by structural topological transformation of layered double hydroxides (LDHs) precursor, which displayed promising catalytic behavior toward CTH reaction of furfural (FAL) with 2-propanol (2-POL) as the hydrogen donor. Notably, the reaction rate is as high as 0.125 mol g −1 h −1 , which is superior to previously reported non-noble metal catalysts. A combination investigation based on XPS, XANES and Bader charge confirms the co-existence of Cu 0 and Cu + sites on the surface of Cu nanoparticles . Both experimental studies ( in situ DRIFTS and isotope labelling MS) and DFT calculations reveal that the Cu 0 − Cu + synergistic effect plays a vital role in determining catalytic behavior: the Cu + species acts as both dehydrogenation and hydrogenation active site; while the Cu 0 site promotes the transfer of H atoms between adsorbed substrates. This work substantiates a Cu 0 −Cu + synergetic catalysis by establishing structure-property correlation and revealing reaction pathway, which could be extended to other CTH reactions in the upgrading processes of biomass.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
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2022
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IF 14.224
Xin Liu,Peng Xu,Zhuoyu Yang,Pengfei Zhu,Lei Wang,Shiqi Xie
Cu 0 coupled with O 2 was used to degrade contaminant due to in-site generation and catalysis of H 2 O 2 , while the low reactivity and active dismutation reaction of Cu + refrained the performance at acidic condition. In this study, the removal rate of 4-acetamidophenol increased from 27 % to 83.4 % with Fe 3+ spiked into the Cu 0 system within 60 min •OH was the primary reactive species in the Fe 3+ /Cu 0 system. In the Fe 3+ /Cu 0 system, Cu 0 was corroded to form Cu + by H + and O 2 , and then Cu + interacted with O 2 generating H 2 O 2 , and meanwhile Fe 3+ was reduced to Fe 2+ by Cu + and Cu 0 ; Consequently, Cu + and Fe 2+ induced H 2 O 2 to produce •OH, but Fe 2+ was easier to catalyze H 2 O 2 than Cu + at acidic pH. Except for fulvic acid , common water matrix including sulfate ion, phosphate ion, chloride ion and nitrate ion had no inhibition effect on the degradation of 4-acetamidophenol in the Fe 3+ /Cu 0 system. over 62 % of 4-acetamidophenol in tap water , Hou-lake water and well water was greatly oxidized by the Fe 3+ /Cu 0 system. Furthermore, the amount of total dissolved copper decreased to 0.895 mg/L by the method of alkali precipitation in the Fe 3+ /Cu 0 system. The study provided a theoretical direction to the Fe 3+ -enhanced Cu 0 system for purifying wastewater.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
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IF 13.3
Jie Zhu,Sifan Wang,Jiaji Zhang,Zhecheng Fang,Weitao Ji,Gaobo Lin,Lei Guo,Bolong Li,Jianghao Wang,Jie Fu
Constructing a stable Cu 0 /Cu 2+ interface is critical for enhancing the C-C coupling during the process of CO 2 electroreduction. However, the high-valence Cu species are unstable under the operating conditions. Herein, polyhedral-shaped CuO is coated with hydroxy-rich SiO 2 nanoparticles (m-SiO 2 /CuO) to stabilize the Cu 2+ species, enabling efficient CO 2 reduction to the ethylene product. Significantly, the optimal m-SiO 2 /CuO catalyst exhibits an impressive Faradaic efficiency of 55.5 % and an industrial-level partial current density of 500 mA cm −2 toward ethylene. Fourier transform infrared spectra and X-ray photoelectron spectra reveal that the strong interfacial interaction between CuO and hydroxy-rich SiO 2 is conducive to stabilizing the Cu 2+ species. In-situ characterizations reveal that the Cu 0 /Cu 2+ interface facilitates CO 2 activation and the key intermediate *OCCHO, thus promoting the production of ethylene. This work paves the way for developing advanced electro-catalysts of producing ethylene.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Kejing Wang,Yongjun Liu,Zhiwen Li,Nan Cui,Lei Sun,Wei Huang
The valence states of Cu site are regarded as an important factor affecting the performance of syngas to higher alcohols (C 2+ OH). Regrettably, the role of Cu 0 and Cu + in CO hydrogenation to higher alcohols remains controversial due to the complexity of the reaction. In this study, Cu 0 and Cu 2 O powders are directly added as the precursors to adjust the ratios of Cu + /(Cu 0 +Cu + ) and Cu particle sizes in CuZnAl catalysts by a complete liquid-phase (CLP) technology. The CAT-Cu 0 catalyst with higher Cu 0 content shows the highest CO conversion (>15%) ascribing to the biggest S Cu , but is also accompanied by the highest CO 2 selectivity (>40%), while the CAT-Cu + catalysts with higher Cu + content displays relative better C 2+ OH selectivity (>60%) and stability due to a higher probability of CO insertion. In-situ DRIFTS experiments reveal that a synergy between larger Cu particle sizes (30～40 nm) and surface Cu + sites, in which larger Cu sizes enhances the probability of bridge CO adsorption, thereby favoring the C–O bond dissociation for CH x formation. Meanwhile, Cu + active sites provide a higher probability for CO/CHO insertion to form CH 3 CHO*/CH 2 CO* intermediates. This study further deepens our understanding of the critical controlling factors for highly selective synthesis of C 2+ OH from syngas over Cu-based catalysts.
研究领域:
化学工程
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催化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
SCIENCE OF THE TOTAL ENVIRONMENT
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2020
·
IF 6.551
Yong Liu,Yang Zhao,Jianlong Wang
In this study, a novel Cu 0 -Cu 2 O@CNTs composite was synthesized, characterized and applied to activate peroxydisulfate (PDS) for the degradation of 2, 4-dichlorophenol (2,4-DCP) in contaminated lake water. The results indicated that Cu 0 -Cu 2 O@CNTs can effectively activate PDS to produce O 2 • − radical, which has high selectivity to degrade organic pollutants in actual contaminated water. The efficiency of 2,4-DCP degradation and mineralization was 99.27% and 66.90%, respectively under the optimal condition. In the presence of Cl − , HCO 3 − and natural organic matters (NOMs) or in real wastewater containing 2,4-DCP, Cu 0 -Cu 2 O@CNTs/PDS system had a good selectivity for 2,4-DCP degradation. O 2 • − was the dominant reactive species in Cu 0 -Cu 2 O@CNTs/PDS system for 2,4-DCP degradation. The possible degradation pathway of 2,4-DCP was proposed. It was concluded that Cu 0 -Cu 2 O@CNTs composite could overcome the shortcomings of PDS activation by Cu 0 and Cu 2 O alone, such as low activating capability of Cu 0 and instability of Cu 2 O, which was high efficient for activating PDS. Cu 0 -Cu 2 O@CNTs composite can be used as an efficient catalyst to activate PDS for the degradation of toxic organic pollutants in water and wastewater.
研究领域:
环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Shiyao Lu,Jian Zhang,Hao Meng,Xiaoyuan Qin,Jianbin Huang,Yehao Liang,Feng-Shou Xiao
The direct dehydrogenation of ethyl lactate (EL) to produce ethyl pyruvate (EP) over non-precious heterogeneous catalysts is highly desirable, but challenging. Herein, we report a highly efficient silica-supported copper catalyst prepared via a hydrolysis-precipitation method (Cu/SiO 2 -HP) for the dehydrogenation of ethyl lactate, which exhibited an 85.4 % EL conversion with 91.1 % selectivity toward EP at 320 °C. XAFS, in situ XPS, and CO-adsorption FT-IR spectra revealed that the Cu/SiO 2 -HP catalyst had abundant Cu 0 /Cu + interfaces. In situ FT-IR spectra, kinetic studies , and theoretical calculations also demonstrated that the Cu 0 /Cu + interfaces synergistically activate the O−H and C−H bonds in the adsorbed EL for direct dehydrogenation into EP. The H/D kinetic isotope effect for model reaction confirmed that C−H bond activation is the key step in the dehydrogenation reaction. This study offers a new approach toward the selective conversion of EL into EP, which is of great significance for biomass conversion .
研究领域:
催化
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化学工程
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材料科学
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生物质转化
✓ 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）