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.
研究领域:
催化化学
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材料科学
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氢气储存
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化学反应工程
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表面化学
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高影响因子
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.
研究领域:
电化学
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催化材料科学
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PubMed
高影响因子
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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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.
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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PubMed
高影响因子
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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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.
研究领域:
催化
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材料科学
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化学工程
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纳米技术
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表面化学
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jingyun Zhang,Zhen Jia,Shitao Yu,Shiwei Liu,Lu Li,Congxia Xie,Qiong Wu,Youzheng Zhang,Hailong Yu,Yuxiang Liu,Jinhui Pang,Yue Liu
Controllable carbonyl group (C O) hydrogenation is the key to the transformation of furfural molecules into high-value furfuryl alcohol chemicals. Herein, a non-noble copper metal catalyst (Cu/MgO) was prepared for the efficient hydrogenation of furfural to furfuryl alcohol under mild conditions. At 383 K and 2 MPa H 2 , 99.9% conversion of furfural with 99.9% selectivity to furfuryl alcohol was achieved within 80 min while the turnover frequency (TOF) was 56.87 h −1 . The temperature of a reductive pretreatment can be used to tune the nature of the interfaces between reduced copper and the metal oxides present in copper-magnesium oxide catalysts. The valence copper species exhibited unique catalytic properties in the hydrogenation of furfural to furfuryl alcohol. Besides, the Cu/MgO-350 exhibited excellent stability and reusability without significant activity loss. These results were accounted for by the MgO alkaline interface contributing to the effective formation and high dispersion of different valence Cu species. The active site had strong adaptability to the adsorption of reactants and desorption of products, thus avoiding excessive hydrogenation of furfural. According to the analysis of the characterization data, furfural adsorption mainly existed in η 1 (O)-aldehyde binding mode which was consistent with the density functional theory (DFT) calculation. DFT calculations of the reaction process showed that the theoretical results favored the hydrogenation of furfural through a hydroxyalkyl intermediate rather than of an alkoxide intermediate.
研究领域:
催化化学
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材料科学
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理论计算
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2026
·
IF 9.2
Yanping Dong,Xiqiang Tian,Jinhui An,Pengyu Xu,Xinrui Wei,Muhammad Zahid
Achieving high activity, superior selectivity, and durable performance remains challenging for pristine MOFs in heterogeneous hydrogenation catalysis. Herein, nitrogen-doped carbon-wrapped Cu@Cu 2 O/NC heterogeneous catalysts enriched with Cu 0 –Cu + interfacial sites were readily derived by calcining Cu-MOF under an air atmosphere. Comprehensive characterization was conducted to examine synthesis-induced variations in bulk crystallinity, surface chemistry, and catalytic activity for Cu-MOF-250, Cu-MOF-350, and Cu-MOF-450. Compared to its counterparts, the Cu-MOF-350 catalyst exhibited optimal performance in the preferential hydrogenation of noxious 4-nitrophenol (4-NP) to valued 4-aminophenol (4-AP), maintaining high activity for up to ten consecutive rounds. The enhanced catalytic hydrogenation efficiency of the Cu-MOF-350 catalyst is ascribed to its distinctive nanostructural features, which originate from the synergistic interplay between Cu and Cu 2 O species. In addition, the improved uniform distribution of Cu@Cu 2 O nanoparticles generates higher concentration of interfacial exposed reactive Cu 0 /Cu + sites on the Cu-MOF-350 surface, which are considered crucial for the promoted hydrogenation of 4-NP.
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ChemPhotoChem
·
2025
·
IF 3
Mengrong Zhang,Sha Ni,Zichao Yang,Min Zhang,Zhongjie Guan,Jianjun Yang
Graphical Cu-modified monoclinic TiO 2 nanoflowers with OVs (Cu 1 TB-1.5) promote the reactivity and selectivity of CO 2 reduction to CO under visible light. CO selectivity is 99.6%, and the cycling stability is excellent. The Cu 1 TB-1.5 facilitates the formation of the intermediate COOH* during the photocatalytic process, thus improving the yield and selectivity of CO. The photoreduction of CO 2 has attracted extensive attention as a promising solution to global warming. In this study, Cu-modified TiO 2 (B) (CuTB) nanoflowers with oxygen vacancies (OVs) are designed and synthesized via hydrothermal treatment and photodeposition to promote the reactivity and selectivity of CO 2 reduction to CO under visible light. The CO and CH 4 yields of sample Cu 1 TB-1.5 under visible light are 5.72 and 0.02 μmol g −1 h −1 , wherein the CO yield was 15.5 times that of sample TB; its selectivity is 99.6%, and the cycling stability is excellent. OVs can broaden the light absorption of TB to the visible light region, and Cu promotes photoinduced electron transfer from TB to the Cu species and act as an active center. The OVs and Cu can synergistically enhance charge separation, CO 2 adsorption, and CO 2 conversion. The Cu 1 TB-1.5 facilitates the formation of the intermediate COOH* during the photocatalytic process, thus improving the yield and selectivity of CO. This research provides a unique idea for the development of novel highly selective photocatalysts.
研究领域:
材料科学
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环境科学
·
化学工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Wen-Jing Yi,Jingyi Yang,Yongzhen Gao,Xiaotian Zhou,Wenlei Zhang,Meng Zhang,Zhongyi Liu
Copper catalysts have garnered considerable interest as promising active metals for upgrading biomass resources, especially in selective furfural (FF) hydrogenation reaction. However, effectively enhancing the interactions between active metals and supports while providing abundant surface reaction sites remains enormous challenge to improve catalytic performance. Herein, we present a unique hydrotalcite-derived Cu-based catalyst featuring well-dispersed Cu 0 /Cu + nanodots towards selectively hydrogenated FF to furfuryl alcohol (FA). Impressively, the optimized CuMg 3 Al-R catalyst exhibits the exceptional hydrogenation performance, achieving almost 100 % FF conversion and 99.3 % FA selectivity. Comprehensive studies reveal that the small sized Cu species with well dispersion, the synergistic effect of Cu 0 and Cu + , combined with the selective adsorption and activation of C O groups jointly contribute to the enhanced catalytic performance. This work offers a promising strategy to rationally design well-dispersed Cu species for the selective hydrogenation of C O groups, which holds great significance for biomass-related hydrogenation reaction.
研究领域:
催化化学
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生物质能
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材料科学
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高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 3
·e202502450
·
IF 5.9
Mengmeng Jin,Yaolei Zhao,Weiting Li,Tiantian Xu,Jiazuo Wei,Jingjun Liu
2,5-Bis(hydroxymethyl)furan (BHMF) is a promising intermediate for the synthesis of pharmaceuticals and crown ethers, whereas achieving a high reaction rate in the hydrogenation of 5-hydroxymethylfurfural (5-HMF) to form BHMF remains challenge. In this work, a series of Cu/CeO 2 –x catalysts ( x denotes H, Air, Ar) were synthesized by calcination under different atmospheres (10% H 2 /Ar, Air, Ar) and evaluated for the 5-HMF hydrogenation to BHMF. Cu/CeO 2 –Ar exhibited a superior reaction rate of 26.8 mmol·g cat −1 ·h −1 and BHMF yield of 99.1% under the condition (180°C, 5 h, 1 MPa H 2 ), significantly outperforming Cu/CeO 2 –H and Cu/CeO 2 –Air. The characterizations reveal that the calcination in the oxygen-deficient argon atmosphere led to high Cu dispersion and minimized Cu particle size in the Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + –O V –Ce 3+ sites and increased Cu 0 number. In situ Fourier transform infrared spectroscopy analysis elucidates the distinct roles of these active sites. Cu + sites are responsible for perpendicular adsorption of the 5-HMF carbonyl group, and Cu 0 sites drive efficient H 2 dissociation. In contrast, the O V –Ce 3+ sites do not adsorb 5-HMF and H 2 . The close synergy between numerous Cu 0 sites and abundant Cu + sites in the Cu/CeO 2 –Ar accelerates the process of 5-HMF hydrogenation to BHMF. Graphical The oxygen-deficient argon atmosphere led to high dispersion and small particle size of Cu in Cu/CeO 2 –Ar. These properties resulted in the abundant Cu + sites for the adsorption of CO from 5-HMF and the numerous Cu 0 sites to efficiently dissociate H 2 , synergistically boosting catalytic reaction rate to 26.8 mmol·g cat -1 ·h -1 .
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高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Shangpu Zhuang,Yilin Lei,Fan Xue,Tao Wei,Jiahui Chu,Mifen Cui,Zhuxiu Zhang,Ruiping Wei,Jihai Tang,Xu Qiao
Unraveling the synergistic interplay between Cu 0 /Cu + and support sites in Cu-based catalysts, coupled with oxygen vacancy-mediated active site modulation and their impact on hydrogenation performance metrics, remains a critical challenge in heterogeneous catalysis. Herein, we engineered a family of MOF-derived Cu/CeO 2 catalysts with tunable Cu loadings and oxygen vacancy(O V ) concentrations, featuring Cu 0 -Cu + -O V interfacial sites, through a MOF-mediated pyrolysis strategy. Operando DRIFTS, XPS, and Raman analyses revealed dynamic restructuring of active sites during hydrogenation of cyclohexyl acetate. The optimized catalyst achieved 98.0 % substrate conversion and 97.3 % cyclohexanol selectivity at 250 ℃ under 3 MPa H 2 , exhibiting a TOF 2.8-fold higher than conventional Cu/CeO 2 . The results indicate that the superior catalytic performance of Cu/CeO 2 -MOF should be attributed to the synergistic effects of Cu + , Cu 0 , and O V . This synergy enhances the ability of catalysts to adsorb and activate cyclohexanone, as well as its hydrogen dissociation capability. Further analysis indicates that O V exerts a direct influence on product selectivity. Moreover, the concentration of O V modulates the ratio of Cu + /(Cu + +Cu 0 ), which significantly affects conversion efficiency of the reaction. This work introduces an innovative approach to designing the electronic structure of copper-based catalysts, thereby optimizing the hydrogenation reactions of carbonyl compounds.
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