INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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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.
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JOURNAL OF POWER SOURCES
·
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.
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Nature Communications
·
2025
·
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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CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xingyue Yang,Lei Wang,Shijie Zhou,Shilong Zhang,Yongfang Xu,Yujie Bian,Zhaowei Tian,Yusen Yang,Min Wei
Liquid organic hydrogen carriers (LOHC), which involve reversible catalytic hydrogenation/dehydrogenation cycles, have attracted considerable attention. This study investigates Cu/CuAlO x catalysts with unique Cu 0 –Cu + interfacial sites, which are prepared via structural topological transformation of layered double hydroxide (LDH) precursors. The optimized Cu/CuAlO x catalysts exhibit exceptional catalytic activity in 1,2,3,4-tetrahydroquinoline (THQ) dehydrogenation, achieving a complete conversion of THQ within 1.5 h and a turnover frequency (TOF) value amounts to 19.94 h −1 at 150 °C, which stands at the highest echelon compared with previously reported heterogeneous catalysts. Furthermore, the catalyst also exhibits excellent performance in quinoline hydrogenation (yield >99 %) after 6 h at 60 °C, and the TOF value reaches up to 7.01 h −1 . A comprehensive investigation based on XPS, TEM and XAFS verifies the dual active states Cu 0 and Cu + sites coexisting on nanoparticle surfaces. Both experimental studies ( in situ DRIFTS and XPS) and DFT calculations reveal the pivotal role of the Cu 0 − Cu + synergistic effect in dictating catalytic behavior: the Cu + species preferentially adsorb and activate the N − H bonds and C − H bonds in N-heterocycles; Whereas the Cu 0 site facilitates efficient reassociation of surface adsorbed H atoms and product desorption (H 2 ). This work exhibits substantial potential for implementation in hydrogen storage technologies, offering a viable pathway towards efficient LOHC utilization in clean energy systems.
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Journal of Materials Chemistry A
·
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.
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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.
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Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Meng Hao,Yang Yusen,Shen Tianyao,Yin Zhiming,Wang Lei,Liu Wei,Yin Pan,Ren Zhen,Zheng Lirong,Zhang Jian,Xiao Feng-Shou,Wei Min
Copper-based catalysts serve as the predominant methanol steam reforming material although several fundamental issues remain ambiguous such as the identity of active center and the aspects of reaction mechanism. Herein, we prepare Cu/Cu(Al)O x catalysts with amorphous alumina-stabilized Cu 2 O adjoining Cu nanoparticle to provide Cu 0 −Cu + sites. The optimized catalyst exhibits 99.5% CH 3 OH conversion with a corresponding H 2 production rate of 110.8 μmol s −1 g cat −1 with stability over 300 h at 240 °C. A binary function correlation between the CH 3 OH reaction rate and surface concentrations of Cu 0 and Cu + is established based on kinetic studies. Intrinsic active sites in the catalyst are investigated with in situ spectroscopy characterization and theoretical calculations. Namely, we find that important oxygen-containing intermediates (CH 3 O* and HCOO*) adsorb at Cu 0 −Cu + sites with a moderate adsorption strength, which promotes electron transfer from the catalyst to surface species and significantly reduces the reaction barrier of the C−H bond cleavage in CH 3 O* and HCOO* intermediates.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Bowen Wang,Lu Song,Chen Peng,Ximeng Lv,Gengfeng Zheng
The acidic CO 2 reduction reaction (CO 2 RR) offers a promising approach to mitigate CO 2 reactant loss and carbonate deposition, which are challenging issues in alkaline or neutral electrolytes. However, the hydrogen evolution reaction (HER) competes in the proton-rich environment near the catalyst surface as a side reaction, reducing the energy efficiency of generating multi-carbon (C 2+ ) products. In this work, we proposed a palladium (Pd) doping strategy in a copper (Cu)-based catalyst to stabilize polarized Cu 0 -Cu + sites, thus enhancing the C C coupling step during the CO 2 RR while suppressing HER. At an optimal doping ratio of 6%, the Pd dopants were well dispersed as single atoms without aggregation, allowing for the stabilization of subsurface oxygen (O Sub ), preserving the polarized Cu 0 -Cu + active sites, and reducing the energy barrier of C C coupling. The Pd-doped Cu/Cu 2 O catalyst exhibited a peak Faradaic efficiency (FE) of 64.0% for C 2+ products with a corresponding C 2+ partial current density of 407.1 mA∙cm −2 at −2.18 V versus a reversible hydrogen electrode, a high CO 2 single-pass conversion efficiency (SPCE) of 73.2%, as well as a high electrochemical stability of ∼ 150 h at industrially relevant current densities, thus suggesting a potential approach for tuning the electrocatalytic CO 2 performances in acidic environments with higher carbon conversion efficiencies.
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CATALYSIS LETTERS
·
2026
·Vol. 156
·期 8
·229
·
IF 2.5
Sun Zeyun,Wang Jiapan,Pu Weijia,Liu Yang,Xiao Yahui,Pu Yanfeng,Zhao Junwei,Liu Yong
The hydrogenation of esters to corresponding alcohols is a crucial yet challenging process in sustainable chemistry, demanding efficient and stable non-noble metal catalysts. In this study, a CuZnO x /CeO 2 metal-oxide catalyst was synthesized via a metal-organic framework (MOF)-derived route for the hydrogenation of cyclohexyl acetate. The catalyst, featuring highly dispersed Cu species and low Cu loading (11.4wt%), was obtained by calcining a Ce-MOF precursor incorporated with Cu and Zn. By modulating the reduction temperature, the mixed valence state Cu 0 and Cu + active species were observed to coexist on the catalyst surface. After systematic investigation of structure-activity relationship in catalytic hydrogenation, and the optimized CuZnO x /CeO 2 -400-350 catalyst reached 99.9% conversion of cyclohexyl acetate, with selectivity of 98.2% to cyclohexanol under mild conditions (240 °C, 3 MPa H 2 , 11.4 wt% Cu loading in actual, 4 h). Moreover, it exhibited outstanding recyclability, maintaining over 99.0% conversion and above 97.0% cyclohexanol selectivity after five cycles. XRD and XPS analyses revealed no significant changes in the crystal structure or Cu 0 /Cu + species after reaction, confirming excellent resistance to sintering and remarkable structural stability. This work affords a feasible way for designing high-performance catalysts for ester hydrogenation, demonstrating significant potential for industrial application. Graphical
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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 .
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Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
Lu Yuxuan,Yue Feng,Liu Tianyang,Huang Yu-Cheng,Fu Feng,Jing Yu,Yang Hengquan,Yang Chunming
The synergistic Cu 0 -Cu + sites is regarded as the active species towards NH 3 synthesis from the nitrate electrochemical reduction reaction (NO 3 - RR) process. However, the mechanistic understanding and the roles of Cu 0 and Cu + remain exclusive. The big obstacle is that it is challenging to effectively regulate the interfacial motifs of Cu 0 -Cu + sites. In this paper, we describe the tunable construction of Cu 0 -Cu + interfacial structure by modulating the size-effect of Cu 2 O nanocube electrocatalysts to NO 3 - RR performance. We elucidate the formation mechanism of Cu 0 -Cu + motifs by correlating the macroscopic particle size with the microscopic coordinated structure properties, and identify the synergistic effect of Cu 0 -Cu + motifs on NO 3 - RR. Based on the rational design of Cu 0 -Cu + interfacial electrocatalyst, we develop an efficient paired-electrolysis system to simultaneously achieve the efficient production of NH 3 and 2,5-furandicarboxylic acid at an industrially relevant current densities (2 A cm −2 ), while maintaining high Faradaic efficiencies, high yield rates, and long-term operational stability in a 100 cm 2 electrolyzers, indicating promising practical applications.
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Yue Chen,Yu Ma,Chen Liao,Jiacheng You,Huihuang Fang,Chongqi Chen,Yu Luo,Lilong Jiang
The construction and stabilization of Cu–O–Si interfaces in copper-based catalysts remain critical yet challenging for the water-gas shift reaction (WGSR), as conventional strategies fail to mitigate copper nanoparticle (NP) aggregation and interfacial instability. This study innovatively proposes a spatial confinement strategy by anchoring Cu NPs inside (Cuin/SBA-15) or outside (Cuout/SBA-15) the mesoporous channels of SBA-15, leveraging nanoscale confinement to optimize Cu–O–Si interfaces. The confined Cuin/SBA-15 catalyst demonstrated exceptional WGSR performance, achieving a reaction rate of 5.4 μmolCO·gcat−1·s−1, significantly surpassing conventional Cu/SBA-15 (3.1 μmolCO·gcat−1·s−1) and surface-loaded Cuout/SBA-15 (2.8 μmolCO·gcat−1·s−1), along with remarkable stability. This enhancement originates from the SBA-15 channels enabling the in situ formation of stable Cu–O–Si interfaces, which regulate the dynamic equilibrium between Cu0 (active for H2O dissociation) and Cu+ (critical for CO adsorption) species. In situ studies revealed their synergistic dynamic interconversion during WGSR, while domain confinement effects suppressed sintering by maintaining interfacial integrity. Kinetic and mechanistic analyses further identified the associative pathway, with HCOO* intermediate dissociation as the rate-determining step, facilitated by the stabilized Cu–O–Si interfaces. By resolving interfacial instability through confinement engineering, this work provides a paradigm for designing robust Cu-based catalysts, advancing both fundamental understanding and practical applications in WGSR and related heterogeneous catalysis.
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