MATERIALS CHEMISTRY AND PHYSICS
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2025
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IF 4.7
Haozhe Pang,Shimao Shangguan,Ya Chen,Yue Zhang,Siyuan Fan,Lida Shen,Zongjun Tian,Zhidong Liu
Bronze, as a solid self-lubricating material, is widely used in various frictional applications. However, under increasingly common high-frequency and high-load conditions, particularly in the absence of lubricants, bronze layers are prone to rapid wear. Incorporating MoS 2 particles to fabricate solid self-lubricating composite coatings is considered a promising approach to improve overall performance in harsh environments. In this study, a friction-assisted jet electrodeposition process is employed to fabricate Cu-Sn-MoS 2 composite coatings. This technique enhances particle embedding and surface leveling, producing uniform and dense coatings with significantly improved tribological performance. The methodological framework of this study involves the fabrication of Cu-Sn-MoS 2 composite coatings via friction-assisted jet electrodeposition, followed by systematic characterization of their surface morphology, microhardness, adhesion, and tribological behavior. The results show that a MoS 2 content of 5 g/L provides a uniform and compact surface with fine grains, sufficient microhardness and adhesion strength, and a continuous lubricating film formed during wear. The wear mechanism was revealed to explain why the Cu-Sn-MoS 2 coating exhibited a strong performance in mechanical properties and wear resistance. This content achieves the lowest friction coefficient and the best wear resistance among all tested compositions.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Liping Du,Limo He,Song Hu,Sheng Su,Yi Wang,Long Jiang,Jun Xu,Kai Xu,Jun Xiang
The low-temperature water-gas shift (WGS) reaction confronts critical challenges of sluggish kinetics, inadequate H 2 yield and CO conversion, necessitating the development of high-activity catalysts to effective clean energy production with reduced energy consumption. In this study, we systematically investigate the relationship between the physicochemical properties of Cu-based catalysts supported on CeO 2 with tailored morphologies (nanorods, nanospheres, and nanocubes) and catalytic performance. Cu-CeO 2 (R) achieves 52.3 % CO conversion and 79.88 mL/gH 2 O H 2 production at 370 °C—nearly twice those of Cu-CeO 2 (P) under identical conditions—with an apparent activation energy of 55.25 kJ·mol −1 . This outstanding performance stems from proper oxygen vacancy concentration (OVC, 2.23 × 10 21 cm −3 ) and ordered Cu + -[O v ] Ce 3+ interfacial sites induced by strong metal-support interaction (SMSI) within Ce 1-x Cu x O 2 solid solutions. In contrast, Cu-CeO 2 (S) and Cu-CeO 2 (C) display relatively lower maximum CO conversions (45.97 % at 410 °C and 43.7 % at 370 °C, respectively), due to excessive defect oxygen (34.41 % and 44.89 %) that strongly adsorbs reaction intermediates, postponing the WGS rate by 15–20 %. In-situ spectroscopy reveals that CeO 2 morphology modulates oxygen vacancy (O v ) distribution and Cu Ce interfacial structures, giving rise to distinct adsorption states and binding strengths of CO/CO 2 on Cu/CuO x nanoclusters with varied valence states and dispersions. Cu-CeO 2 (S) and Cu-CeO 2 (C) exhibit complex carbonation pathways, featuring dynamic evolution of intermediates from monodentate to bidentate to polymeric carbonates, attributed to surface site diversity and cross-interactions of Cu sites. This work elucidates the morphology-activity relationship of Cu-CeO 2 catalysts, providing insights for the rational design of highly active low-temperature WGS catalysts.
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PubMed
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SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Yaqi Wu,Jianhua Qian,Yanan Wang,Jinjuan Xing,Junhua Li,He Huang,Xueming Kang,Jiasheng Xu
Developing transition metal oxide-based catalysts with both high thermal stability and catalytic activity for the effective volatile organic compounds (VOCs) removal remains a major challenge in heterogeneous catalysis. In this work, a series of Cu, Mn, Co and Ni substituted Co 3 O 4 spinel catalysts with a large number of oxygen vacancies were produced as extremely stable and active substances for the oxidation of toluene. The CuCo 2 O 4 catalyst, prepared through transition metal substitution, demonstrated exceptional performance with T 50 , T 90 , and complete conversion temperatures of 204 °C, 220 °C, and 228 °C, respectively. Furthermore, the CuCo 2 O 4 catalyst displayed markedly enhanced thermal stability compared to other catalysts, which was crucial for practical implementation. Its superior catalytic activity originated from electron transfer between Co and Cu cations, facilitated by lattice oxygen, which increased the Co 3+ /Co 2+ ratio. This structural modification strengthened oxygen migration and reducibility within the spinel framework, facilitating efficient regeneration of lattice oxygen and rapid activation of adsorbed oxygen species. Kinetic analyses corroborated these findings, revealing that CuCo 2 O 4 possessed the lowest activation energy ( E a = 40.40 kJ/mol), thereby reducing the energy barrier for toluene oxidation. These results demonstrate that the CuCo 2 O 4 catalyst represents a promising candidate for practical applications, combining high catalytic activity for toluene oxidation with exceptional operational durability and thermal stability.
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Journal of Energy Chemistry
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2025
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IF 14.9
Yaqing Hu,Mingxia Zhou,Kunyu Xu,Zihao Yang,Zhaoxia Dong
The electroreduction of carbon dioxide to multi-carbon products (C 2+ ) represents an effective pathway for achieving carbon cycling and high-density renewable energy storage. However, its practical implementation is challenged by excessively high C–C coupling reaction energy barriers and competitive hydrogen evolution reaction (HER). Modifications to the local microenvironment play a decisive role in the three-phase interface reaction of CO 2 electrocatalytic reduction. Therefore, this study employed an Al 2 O 3 -modified copper catalyst (Al 2 O 3 /Cu) to modulate the local reaction microenvironment, thereby promoting C 2+ formation. Notably, the optimized Al 2 O 3 /Cu catalyst achieved a remarkable C 2+ Faraday efficiency (FE) of 71.3% at −1.33 V vs. RHE (reversible hydrogen electrode; all potentials herein are referenced to RHE) in a neutral electrolyte using a flow cell, significantly outperforming unmodified Cu catalysts. This catalyst also demonstrated excellent catalytic stability, exceeding 56 h. Theoretical calculations and in situ spectroscopic characterization confirmed that introduced Al 2 O 3 species kinetically facilitate water dissociation and proton consumption, which is crucial for maintaining a transient localized high-pH environment under operating conditions. This alkaline microenvironment not only suppresses the HER but also stabilizes the critical Cu 2+ /Cu + active sites against over-reduction, while simultaneously lowering the energy barrier of C–C coupling reactions. This work underscores the critical role of dynamically modulating the localized chemical environment in neutral electrolytes for CO 2 reduction reactions (CO 2 RR), offering novel insights for designing such microenvironments.
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CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Xin Wang,Qinian Wang,Mu Yuan,Xu Cheng,Bo Zhang,Ke Zhang,Lili Wang,Chao Wu,Xing Zhang
Electrochemical reduction of NO 3 – (ERN) is a promising route for sustainable water treatment and nitrogen recovery. However, its practical implementation is hindered by the low Faradaic efficiency (FE) and NH 4 + yield rate of conventional electrodes under low NO 3 – concentrations (≤50 mg-N L -1 ). These limitations primarily arise from insufficient reactant accessibility and the undesired hydrogen evolution reaction (HER). Here, we developed a copper electrode modified with polyvinylpyrrolidone (PVP) and grain boundary (GB) defects as an ERN catalyst (denoted as PVP-Cu). The PVP-Cu electrode achieved a FE of 81.82 % and an NH 4 + yield rate of 0.44 mg-N h −1 cm −2 , approximately 3-fold higher than its counterparts in a 30 mg-N L -1 NO 3 – solution. Characterization results reveal that both PVP modification and GB defects synergistically enhance the triple microenvironment. Specifically, (i) the hydrophilic PVP layer enhances mass transfer, concentrating NO 3 – near active sites, (ii) GB defects facilitate water dissociation, and (iii) these features produce active hydrogen species while suppressing their recombination into undesired H 2 . This integrated “enrichment-activation-suppression” mechanism significantly improves the ERN performance. Additionally, the PVP-Cu electrode exhibited robust resistance to environmental interferences, a widely pH range, minimal Cu leaching, and excellent operational stability. This work establishes a general microenvironment engineering strategy to enhance ERN performance, advancing technologies suitable for decentralized water purification and nutrient recovery.
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JOURNAL OF CATALYSIS
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2025
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IF 6.5
Juan Chen,Linmeng Wang,Hongyi Gao,Rushuo Li,Zhiyuan Liu,Tao Ban,Shunzheng Zhao,Jichao Yang,Ge Wang
Single-atom catalysts (SACs) catalysts have unique electronic properties and geometric structures, offering maximum atom-utilization efficiency. Noble metal-free SACs anchored within metal–organic frameworks (MOFs) enable precise tuning of electronic structures and significantly enhance catalytic activity beyond conventional porous materials. Herein, we synthesized the synthesis of Cu(I)/Ce-MOF-808-EA by anchoring atomically dispersed Cu(II) species onto the open Ce 6 nodes of the Ce-MOF-808 framework, followed by in situ reduction to Cu(I) via ethanol treatment and thermal activation processes. The atomic dispersion and valence transformation of Cu sites on Ce-MOF-808 were confirmed by X-ray Absorption Spectroscopy (XAS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and X-ray photoelectron spectroscopy (XPS). The resulting Cu(I)/Ce-MOF-808-EA exhibited outstanding catalytic performance for the hydrogenation of Dicyclopentadiene (DCPD), achieving 100 % conversion, 91.54 % selectivity toward Dihydrodicyclopentadiene (DHDCPD), and 8.45 % selectivity toward Tetrahydrodicyclopentadiene (THDCPD) at 100 °C, 2 MPa. Notably, Cu(I)/Ce-MOF-808-EA outperformed other transition metal catalysts (Co/Ce-MOF-808-EA, Ni/Ce-MOF-808-EA and Zn/Ce-MOF-808-EA). For the first time, Density Functional Theory (DFT) calculations, combined with experimental investigations, revealed a low-energy reaction pathway for DCPD hydrogenation, wherein Cu(I) sites, in cooperation with adjacent oxygen atoms, act as bi-active centers to heterolytically cleave H 2 into proton and hydride species (*H δ+ -H δ- ) for subsequent hydrogenation. This study underscores the potential of MOFs as versatile platforms for engineering single-atom catalysts with enhanced catalytic properties.
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JOURNAL OF MATERIALS SCIENCE
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2025
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IF 3.9
Fang Qi,Luo Chongwen,Guo Xiaohuan,Cai Bingbing,Zhou Yuzhu,Hu Kun,Wen Changchun
Chemodynamic therapy (CDT) uses the Fenton reaction to generate highly toxic hydroxyl radicals (∙OH) to achieve efficient treatment strategies for tumors. However, the high concentration of glutathione (GSH) in the tumor microenvironment (TME) can scavenge these radicals, thereby diminishing the efficacy of CDT. In this study, we propose a programmable synergistic therapeutic strategy that depletes GSH during chemotherapy (CT) and subsequently increases the production of reactive oxygen species (ROS) to achieve high-potency CDT. We constructed a Cu-Q@Co/ZIF-8 (CQZ) composite nanoplatform by encapsulating cobalt-doped ZIF-8 (Co/ZIF-8) with copper-quercetin (Cu-Q, CQ). The construction of nanoplatform significantly enhanced the water solubility of Co/ZIF-8 and CQ. When the nanoplatform reached the tumor site, the TME triggered the release of quercetin and Cu 2+ from CQ, thus enabling quercetin-based chemotherapy and Cu 2+ -mediated GSH depletion while generating Cu + . Subsequently, the Co 2+ released from Co/ZIF-8 acted with Cu + to catalyze a Fenton-like reaction with endogenous H 2 O 2 , efficiently producing toxic ∙OH radicals for CDT. Throughout the treatment process, Cu 2+ was preferentially released in response to the TME to consume GSH, not only generating Fenton-active Cu + but also preventing the GSH-mediated scavenging of ∙OH. This procedural mechanism has substantially enhanced the therapeutic efficacy of CDT following CT.
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CHEMICAL ENGINEERING SCIENCE
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2025
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IF 4.3
Wenbin Huang,Kaining Wang,Han Yang,Tianyu Bai,Yasong Zhou,Qiang Wei,Minghan Han
CO 2 hydrogenation to methanol emerges as a promising strategy, offering a dual advantage of carbon dioxide fixation and the production of a valuable liquid fuel and chemical feedstocks. However, its industrial application is limited by the high stability of the CO 2 molecule, resulting in low CO 2 conversion and methanol selectivity. In this work, a series of Ce-doped Cu-ZrO 2 catalysts were synthesized by an oxalic acid gel co-precipitation method, and the effect of Ce/Zr molar ratios on catalyst structure and catalytic performance were investigated. Comprehensive characterization techniques, including XRD, N 2 physical adsorption–desorption, HRTEM, H 2 -TPR, XPS, CO 2 /H 2 -TPD and DFT calculation were employed to analyze the influence of Ce doping on oxygen vacancy concentration, surface basicity distribution, electron transfer, and catalytic performance. The results demonstrate that the CC 0.4 Z catalyst (n(Ce)/n(Zr) = 0.4) forms a Ce 0.4 ZrO solid solution structure, significantly enhancing CuO dispersion and generating abundant Cu δ+ -Ce 0.4 ZrO interfacial sites and oxygen vacancies. These features synergistically promote CO 2 /H 2 adsorption and activation while stabilizing Cu + species. Under optimized reaction conditions (260 ℃, 3.0 MPa, 9000 h −1 ), the CC 0.4 Z catalyst exhibits outstanding performance: CO 2 conversion of 14.6 %, methanol selectivity of 74.1 %, and a methanol yield of 10.8 %. Compared to the unmodified catalyst, this represents an increase of 5.8 percentage points in CO 2 conversion and 6.3 percentage points in methanol yield, providing a novel catalyst design strategy for efficient CO 2 conversion.
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Waste and Biomass Valorization
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2024
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IF 2.6
Luo Bo,Liu Huiyu,Shan Rui,Zhang Jun,Yuan Haoran,Chen Yong
Purpose This work aims to investigate the thermal behavior and kinetic characteristics of polyethylene (PE) pyrolysis over Cu/Ce modified ZSM-5. The influences of metal types, particles size of active center and interaction of Cu–Ce species on products distribution are elucidated. Methods Metal-modified ZSM-5 catalysts were prepared by negative pressure impregnation method. Catalytic fast pyrolysis and thermogravimetric experiments were conducted using Py–GC/MS and TG/MS for the qualitative and quantitative analysis of pyrolysis products. Results Morphology characterization indicated the interaction of Cu–Ce species facilitated the regulation of active center size into a nanoparticle scale. The final products were restricted to a carbon number of less than 9 over CuCe/ZSM-5. Cu–Ce modification increased the aliphatic content from 58.5 to 76.1%. Kinetic analysis revealed a remarkable reduction in activation energies during both the intermediate and final stages, where an average decrease of 30% was achieved. Conclusion The synergistic effects of Cu 0 and CeO x facilitated the formation of more short chain olefins by enhancing C–C bonds cleavage activity. Undesired polycyclic aromatic hydrocarbons (PAHs) were avoided by the optimal steric hindrance of CuCe/ZSM-5. Graphical Abstract
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DALTON TRANSACTIONS
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2025
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IF 3.3
Xue-Qing Xu,Shen Yu,Xing-Yu Yue,Zhan Liu,Jia-Min Lyu,Yi-Long Wang,Zhi-Yi Hu,Yu Li,Li-Hua Chen,Bao-Lian Su
Phenol is an important intermediate for high value chemicals. Current phenol production via a three-step cumene process causes severe energy-waste and environmental problems. The conversion of benzene to phenol under mild condition can be achieved by oxidation with Cu-based zeolites. However, conventional microporous zeolite suffers from severe diffusion limitation, especially when bulky molecules are involved, such as benzene. In this work, we used a hierarchically macro-meso-microporous ZSM-5 single crystal (Hier-ZSM-5) as substrate for Cu species (Cu@Hier-ZSM-5). Irregular morphology of opal-like Hier-ZSM-5 exhibits abundant surface Si-OH groups and provides a platform for stabilizing Cu2+ sites. Meanwhile, hierarchical porosity provides significantly improved diffusion ability of bulky molecules. As a result, excellent selective oxidation performance of benzene was obtained with the Cu@Hier-ZSM-5, achieving a conversion of 77% and a phenol selectivity of 73%, which is 1.5 times and 2 times of these obtained with a catalyst based on a microporous ZSM-5, respectively. Species of CuOOH were identified as an important intermediate for benzene oxidation. This hierarchical zeolite system with a synergistic effect of site anchoring and molecular diffusion presents an excellent platform for catalyst design.
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ACS Applied Energy Materials
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2025
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IF 5.5
Yunyun Lin,Wenbo Li,Yuanyuan Cui,Yaying Li,Haifeng Wang,Qi Xiao,Wei Luo
Monolithic photocatalysts present a transformative paradigm to reconcile the activity-stability-recovery trade-off inherent in conventional powder systems for photocatalytic hydrogen evolution. This study demonstrates a low-temperature synthesis of mesoporous Pt/Cu/TiO2–N catalysts in situ grown on frosted glass (Pt/Cu/TiO2–N/FP), where nitrogen doping amplifies Ti–O–Ti vibrational coupling and the hierarchical mesostructure creates sufficient active sites. The engineered Pt–Cu dual-cocatalyst system achieves exceptional synergy: Pt nanoparticles drive proton reduction while Cu2+ species prolong charge carrier lifetime through the Cu2+/Cu+ redox cycle, collectively enabling light absorption to the visible range. With optimized dual cocatalyst decoration (1.1 wt % Pt, 0.3 wt % Cu2+), the monolithic mesoporous architecture delivers a stable hydrogen evolution rate of 187.1 μmol h–1. Importantly, our mild fabrication strategy (NH3 treatment at 100 °C, Cu2+ grafting at 60 °C) establishes a generalizable protocol for temperature-sensitive substrate functionalization. This work pioneers a dual-engineering approach combining substrate-compatible synthesis with electronic structure modulation, offering a pathway toward industrially viable solar hydrogen reactors.
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BIOMASS & BIOENERGY
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2025
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IF 5.8
Yin Wang,Mingqin Xue,Fei Ge,Wenlin Xu,Jianchun Jiang,Minghao Zhou
5-Hydroxymethylfurfural (HMF) played a crucial role in the selective hydrodeoxygenation (HDO) of 2,5-dimethylfuran (DMF). In this work, a series of Cu-MOF-based catalysts were synthesized and applied to the catalytic transfer hydrodeoxygenation (CTHDO) of HMF to produce DMF. Catalyst 2Cu/1BTC-700 exhibited the best catalytic performance, achieving a DMF yield of 95.84 % at 180 °C using isopropanol as the hydrogen donor. Results of detailed characterizations showed the excellent catalytic performance was attributed the appropriate specific surface area, acid sites, the smallest particle size and the synergistic effect between Cu 0 and Cu + species. Mechanistic studies revealed metallic Cu 0 promoted isopropanol dehydrogenation, generating active hydrogen to initiate the CTHDO reaction of HMF, while Cu + acted as Lewis acid sites promoting the activation of the C=O bond and subsequent C–OH cleavage. In addition, the catalyst also had a good reusability, which could give some insights to the high value conversion of HMF.
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