INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2024
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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
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DOI
高影响因子
JOURNAL OF POWER SOURCES
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2022
·
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
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可再生能源
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材料科学
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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
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DOI
高影响因子
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
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催化材料科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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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
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产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2020
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IF 7.632
Qian Wang,Zhi Yu,Junting Feng,Paolo Fornasiero,Yufei He,Dianqing Li
The production of biofuel 2,5-dimethylfuran (DMF) from an important biomass platform of 5-hydroxymethyl furfural (HMF) involves a complicated reaction pathway due to the competition of C═O hydrogenation and C–O hydrogenolysis; however, the dependence of formed intermediates and catalytic sites needs to be further identified. Herein, we constructed a highly efficient and selective Cu/ZnO-Al2O3 catalyst via reduction of a CuZnAl-layer double hydroxide (LDH) precursor, aimed for studying the effect of Cu0/Cu+ species on forming different intermediates and their synergetic promotional effect on HMF hydrodeoxygenation. As expected, the dependence of formation of different intermediates on the Cu+/Cu0 ratio was observed; notably, Cu/ZnO-Al2O3 with higher Cu+/Cu0 ratio finally gave 90.1% DMF selectivity at 100% HMF conversion, more selective than CuNi/Al2O3 (59.6%) and Cu/MgO-Al2O3 (75.8%) references. By a combined study of in situ IR experiments, the observed correlation between the reaction intermediates and the Cu0/Cu+ site suggests that Cu0 tends to adsorb the C═O bond as well as hydrogen molecule, while the Cu+ site is preferable to adsorb and activate the C–O bond. With the synergy of dual active sites, the Cu/ZnO-Al2O3 catalyst showed both high activity and selectivity to DMF. This work provides deep insight into the nature of active Cu species in multiple functional group biomass platform transformation.
研究领域:
催化
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化学工程
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生物化学
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材料科学
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产品关联
DOI
高影响因子
Environmental Science-Nano
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2024
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IF 5.8
Jingwei Hong,Wanli Li,Jin Shang,Hiromi Yamashita,Yun Hu
Utilizing electrocatalysis to convert CO2 into high-value industrial raw materials can not only effectively reduce CO2 emissions but also achieve a closed carbon cycle. This method holds great potential for addressing global warming and alleviating the fossil fuel crisis. Here, we report a novel electrocatalyst for CO2 reduction composed of a composite material derived from Cu-MOF74 and Cu2O, synthesized under the regulation of an appropriate amount of KOH. The research results indicate that the unique Cu0/Cu+ interface in Cu-MOF74/Cu2O-350 enhances the adsorption of reaction intermediates, providing more active sites for CO2 reduction. Additionally, the moderate carbonization during the thermal treatment process increases conductivity and enriches the electrochemical active surface area, accelerating the charge transfer rate. Consequently, this composite exhibits excellent CO2 reduction performance. At -1.3 V vs. RHE, the Faraday efficiency (FE) for C2H4 production reached up to 32.48%, which was significantly higher than that of pure Cu2O-350 (9.25%) and Cu-MOF74-350 (15.52%). Even after 6 hours of reaction, the FE for C2H4 remained above 24.52%, reflecting its good stability. Furthermore, we utilized in-situ infrared spectroscopy to study the key intermediates of the relevant reduction products, inferring the possible reaction pathways for the formation of HCOOH and C2H4. This study provides a simple synthesis method for the preparation of high-selectivity MOF-derived composite catalysts for the electrocatalytic reduction of CO2 to value-added chemicals.
研究领域:
电化学
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材料科学
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环境科学
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催化
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Yafei Qu,Wei Zheng,Peichen Wang,Hao Huang,Minxue Huang,Lin Hu,Hui Wang,Qianwang Chen
Electrochemical carbon dioxide reduction reaction (CO 2 RR) is an effective approach to capture CO 2 and convert it into value-added chemicals and fuels, thereby reducing excess CO 2 emissions. Recent reports have shown that copper-based catalysts exhibit excellent performance in converting CO 2 into multi-carbon compounds and hydrocarbons. However, the selectivity to the coupling products is poor. Therefore, tuning CO 2 -reduction selectivity toward C 2+ products over Cu-based catalyst is one of the most important issues in CO 2 RR. Herein, we prepare a nanosheet catalyst with interfaces of Cu 0 /Cu + . The catalyst achieves Faraday efficiency (FE) of C 2+ over 50% in a wide potential window between − 1.2 V to − 1.5 V versus reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits maximum FE of 44.5% and 58.9% towards C 2 H 4 and C 2+ , with a partial current density of 10.5 mA cm −2 at − 1.4 V. Density functional theory (DFT) calculations show that the interface of Cu 0 /Cu + facilitates C C coupling to form C 2+ products, while inhibits CO 2 conversion to C 1 products.
研究领域:
电化学
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催化
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材料科学
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能量转换
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产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
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2023
·Vol. 12
·期 2
·1218-1232
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IF 11.9
Zi-Yang Zhang,Hao Tian,Han Jiao,Xin Wang,Lei Bian,Yuan Liu,Nithima Khaorapapong,Yusuke Yamauchi,Zhong-Li Wang
The electrochemical CO2 reduction reaction (CO2RR) for high value-added multi-carbon product (C2+) production over copper oxide-based catalysts is an important way to realize the carbon cycle. However, developing effective reaction interfaces and microenvironments to improve the Faraday efficiency (FE) and current density of C2+ remains a major challenge. Herein, we construct Cu0–Cu+–NH2 composite interfaces with the assistance of SiO2. Using Cu2O nanoparticles as a model catalyst, a layer of porous SiO2 is first coated on the surface of the particles, and then, a silane coupling agent containing –NH2 is bonded on the surface of SiO2. The strong interaction between SiO2 and Cu2O at the interface induces the oxidation effect of low valent Cu, and even under the CO2RR, part of Cu+ is reduced to Cu0 and part of Cu+ still maintains positive valence, forming the interface of Cu0–Cu+. SiO2 also acts as a bridge between copper species and –NH2 to create a Cu catalyst–NH2 group interface. With the help of the synergistic effect of the composite interfaces, the optimized Cu2O@SiO2–NH2 catalyst achieves a FE of 81.2% for C2+ products with a current density of 292 mA cm−2 at −1.7 V versus a reversible hydrogen electrode. In situ Raman and attenuate total reflectance-infrared absorption spectroscopy spectra show that the interaction between surface –NH2 and CO2 molecules enhances the adsorption and activation process of CO2 and promotes the formation of CO intermediates (*CO). On the Cu0–Cu+ interface, the C–C coupling process between *CO is accelerated, and the two interfaces synergistically promote the generation of C2+ products. This work provides a new strategy for constructing composite interfaces to improve the CO2RR to C2+ products.
研究领域:
电化学
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材料科学
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催化
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可持续能源
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
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2025
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IF 9.2
Yahui Jiang,Haichuan He,Dan Xia,Hongwei Zhang,Shirui Tan,Li Luo,Yifan Kong,Liu Deng,You-Nian Liu
Cu-based catalysts are widely employed in the electrocatalytic CO2 reduction reaction (CO2RR) toward multi-carbon (C2+) products due to their unique electronic structures. However, Cu-based catalysts are prone to reconstruction under working conditions. Self-reduction and undesirable reconstruction have limited the activity and selectivity of these catalysts. Understanding their reconstruction behavior is crucial for elucidating reaction mechanisms and rationally designing catalysts. In this study, Br-doped Cu-base catalysts were employed to investigate the influence of dopants on catalyst surface reconstruction during CO2RR. Characterizations confirmed that during CO2RR, partial Br− leached from the precursor, while residual bromide ions in the Cu matrix created a bromine-rich environment on the catalyst surface, stabilizing Cu0/Cu+ active sites. The reconstructed catalyst exhibited superior selectivity for C2+ products and higher current density. In situ characterization and theoretical calculations demonstrated that the interaction between Br and Cu atoms suppressed complete Cu reduction. Furthermore, the asymmetric coupling pathway via *CO and *CHO intermediates dominated C2+ product formation, with significantly reduced Gibbs free energy of key intermediates compared to undoped CuO. Notably, halogen doping was validated as a universal strategy—Cu–Cl and Cu–F catalysts similarly enhanced C2+ production while exhibiting analogous reconstruction behavior. This study provided deep insights into catalyst surface reconstruction and offered effective strategies for designing high-performance catalysts for CO2RR.
研究领域:
电化学
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催化
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材料科学
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环境化学
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能量转换
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
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IF 4.339
Xinlei Wang,Kui Ma,Lihong Guo,Ye Tian,Qingpeng Cheng,Xueqin Bai,Jingjing Huang,Tong Ding,Xingang Li
Herein, we reduced the ZnO-modified copper phyllosilicate to synthesize a series of Cu/ZnO/SiO 2 catalysts ( x CuZn/SiO 2 ) which were mixed with γ-Al 2 O 3 for dimethyl ether steam reforming (DME SR). The structure and the formation of copper phyllosilicate were systematically characterized by nitrogen adsorption, XRD and IR. The novel synthetic route led to the remarkably high dispersion of copper species and adjustable Cu 0 /Cu + ratio on the catalyst surface, resulting in the superior catalytic performance for DME SR. The amount of Cu 0 and Cu + sites on the catalyst surface was dramatically affected by ZnO loading, and the turnover frequency results indicated that the 4CuZn/SiO 2 catalyst (Cu/Zn = 4) with the Cu 0 /Cu + ratio of 1 showed the highest catalytic performance. The XPS, H 2 -TPR and TEM results revealed the existence of strong interaction between Cu species and ZnO on the reduced 4CuZn/SiO 2 catalyst, which suppressed the reverse water-gas reaction and prevented the sintering of copper.
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
Nature Communications
·
2025
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IF 15.7
Ren Yuqi,Cheng Miao,He Hongbin,You Changjun,Duan Lunbo,Sun Zhenkun,Peng Ruoxuan,Zhu Yuan-Hao,Zhang Hongyang,Zhou Jiancheng,Huang Kai,Guan Jie,Li Naixu
CO 2 -to-hydrocarbon fuel conversion via artificial photosynthesis is limited by catalyst poisoning under high O 2 partial pressures and sluggish C 2 -product formation. Herein, Ru 0.6 Cu 1 (Cu 0 –Cu 1+ )/CeO 2 catalysts with adaptive O 2 tolerance are prepared by O 2 -mediated dynamic interfacial reconstruction. Single-atom Ru doping at Ce lattice sites creates a trigonal prismatic coordination configuration, enabling proton-coupled electron transfer and accelerating H 2 O dissociation. Photothermal effect promotes O 2 -driven self-assembly of Cu 0 –Cu 1+ charge-gradient interfaces within Ru/Cu alloy clusters, thereby optimizing the adsorption behavior of * CHOCO intermediates and restructuring the C–C coupling pathway. Interfacial charge cascade transfer and geometric site synergy thermodynamically shift the product selectivity from C 1 to C 2 , as determined by operando spectroscopy and electronic structure analysis. Under concentrated solar irradiation, the catalyst produces 549 ± 20 μmol·g −1 C 2 H 4 with 74.3% selectivity and 0.5% solar-to-chemical energy conversion efficiency—25-fold higher than that in non-concentrated systems. Dynamic interfacial regulation facilitates precise carbon chain synthesis in complex reaction networks.
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产品关联
DOI
PubMed
高影响因子
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