CHEMICAL ENGINEERING JOURNAL
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2016
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IF 5.31
Yanghe Fu,Lai Xu,Huanmei Shen,Huan Yang,Fumin Zhang,Weidong Zhu,Maohong Fan
The Cu and Co mixed metal–organic frameworks (MOFs) MOF-74(Cu/Co) with different Cu/Co ratios were prepared via a facile one-pot synthesis method and then characterized by means of various techniques. Whatever the Cu/Co ratios in the synthesized MOFs were, both Cu 2+ and Co 2+ could be uniformly distributed in MOF-74. The synthesized MOF-74(Cu/Co) materials were used as catalysts in styrene oxidation with O 2 under solvent-free and mild reaction conditions. The results show that the catalytic properties of MOF-74(Cu/Co) can be tuned by varying the Cu/Co ratio in MOF-74. MOF-74(Cu) has a rather low catalytic activity but an absolute selectivity for benzaldehyde while MOF-74(Co) possesses a relatively higher catalytic activity, leading to the formation of benzaldehyde, styrene epoxide, and phenylacetaldehyde as well as to polystyrene. It is surprising that the incorporation of Cu 2+ in MOF-74(Co) can completely inhibit the polymerization of styrene while the incorporation of Co 2+ in MOF-74(Cu) can significantly enhance the conversion of styrene to benzaldehyde, styrene epoxide, and phenylacetaldehyde. In addition, by increasing the Co 2+ amount in MOF-74(Cu/Co), the conversion of styrene and the selectivity for styrene epoxide and phenylacetaldehyde are increased while the selectivity for benzaldehyde is decreased. Moreover, the catalytic properties of MOF-74(Cu/Co) were compared with those of the physical mixtures of MOF-74(Cu) and MOF-74(Co), demonstrating the synergetic effects of Co 2+ and Cu 2+ in MOF-74(Cu/Co) on the catalytic oxidation of styrene. The current work reveals a strategy to incorporate multiple metal cations into MOFs for enhancing a specific catalytic property or achieving a new catalytic property.
研究领域:
材料科学
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催化化学
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高影响因子
MATERIALS SCIENCE AND ENGINEERING A-STRUCTURAL MATERIALS PROPERTIES MICROSTRUCTURE AND PROCESSING
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2025
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IF 7
Wei Feng,Jian Zhang,Ruxia Liu,Yong Xiao,Guoqiang Luo,Qiang Shen
Particle-reinforced composite fillers allow precise control of joint microstructure to enhance mechanical performance. However, traditional designs often reduce joint deformability and face issues like particle agglomeration and poor interfacial wettability. To overcome these limitations, a micro-network of Cu-Ti reinforcements within the brazing seam via Ag- x TiH 2 composite filler was developed in this work, which enabled the fabrication of high-strength Si 3 N 4 /Cu joints. Optimal results were achieved with the Ag-4TiH 2 filler, wherein a eutectic liquid formed at the Ag-4TiH 2 /Cu interface during the initial brazing stage. Simultaneously, undissolved Ti reacts with Cu to yield submicron Cu 4 Ti 3 -dominated reinforcements. On the Si 3 N 4 surface, hypostoichiometric TiN/TiN 0 . 61 /TiN 0 . 5 nanocrystals grow sequentially, which is beneficial for enhancing interfacial wettability and bonding reliability. A maximum average shear strength of 186.9 MPa was obtained, a 57.6 % improvement over the conventional AgCuTi filler. The fracture mechanism underwent a notable transformation: brittle failure at mixed regions of Si 3 N 4 and the reaction layer in AgCuTi joints was replaced by ductile failure at the interface between the Cu matrix and the brazing seam in Ag-4TiH 2 joints. The Cu 4 Ti 3 -dominated micro-network offers distinct advantages by enabling controllable in-situ growth that prevents agglomeration while maintaining joint deformability through the synergy effect of the abundant retention of ductile Ag(s, s) and decent elastic modulus and yield strength increment, and regulates the interface reaction to yield a thinner Ti-N layer instead of a TiN/Ti 5 Si 3 dual-layer. These features collectively contribute to the notable mitigation of residual stress within Si 3 N 4 /Cu joints.
研究领域:
材料科学
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焊接技术
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陶瓷金属连接
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复合材料
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界面工程
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Ying Chen,Kun Ge,Xing Liang Cheng,Yuling Hu
Cu@CuO@TCPP-Cu heterojunction with electronic bridge was fabricated. • Cu 2+ bridge boosts charge transfer and strengthens interfacial coupling in Cu@CuO@TCPP-Cu. • The heterojunction shows enhanced SERS performance and POD-like catalytic activity. • Dual-target strategies enable sensitive PAT and H 2 O 2 detection for food safety monitoring. Engineering heterojunctions with efficient carrier separation and interfacial charge transfer is crucial for high performance surface-enhanced Raman spectroscopy (SERS) and enzymatic catalytic activity. However, conventional asynchronous synthesized heterostructures suffer from insufficient interfacial contact, which severely restricts charge transfer kinetics and SERS/catalytic response. Here, we rationally engineer a novel flower-layered Cu@CuO@TCPP-Cu heterojunction mediated by an in situ formed “electron bridge” for high sensitivity sensing applications. A facile surface oxidation technique was employed to grow flower-like CuO in situ on a Cu foil, followed by surface-initiated encapsulation of two-dimensional MOF of TCPP-Cu through coordination between TCPP and Cu 2+ ions released from CuO. The dissociated Cu 2+ ions at the interface serve as an “electronic bridge” between CuO and TCPP-Cu, which drastically shortens the charge transfer distance and enhances interfacial coupling. This unique heterojunciton exhibits remarkable synergy in SERS signal enhancement and peroxidase (POD)-like catalytic activity, as confirmed by density functional theory (DFT) calculations. A robust solid-state SERS sensing chip was thereby constructed. Two distinct analytical strategies were subsequently established, including aptamer-mediated specific detection of patulin (PAT) and enzyme mimicking - amplified turn-on SERS assay for quantitative analysis of H 2 O 2 . The as-constructed sensing chip exhibits excellent analytical sensitivity and selectivity, achieving low limits of detection of 0.640 μg/L for PAT and 13.8 μg/L for H 2 O 2 , respectively. Furthermore, the chip successfully identified both analytes in complex food samples with high accuracy. This work provides a versatile engineering strategy for constructing high performance heterojunction toward advanced analytical and food safety applications. Herein, a novel flower-layered Cu@CuO@Cu-TCPP heterojunction is constructed via an electronic bridge strategy. The bridge-mediated interfacial electron transfer synergistically boots peroxidase-like catalytic activity and SERS performance. Integrating aptamer recognition with nanozyme amplified turn-on SERS sensing enables highly sensitive detection of PAT and H 2 O 2 , offering a universal heterojunction design paradigm and broadening applications in food safety monitoring. Download: Download high-res image (166KB) Download: Download full-size image
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APPLIED SURFACE SCIENCE
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2025
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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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高影响因子
Journal of Materials Research and Technology-JMR&T
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2026
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IF 7.3
Bingnan Chen,Junrui Xu,Hua Sun,Xiang Zhang
Graphene/Cu composites have attracted considerable attention because they combine the excellent properties of both Cu and graphene. However, graphene agglomeration, weak interfacial bonding, and insufficient particle contact often lead to poor densification and limited overall performance of the composites. In this work, Cu matrix composites with different GO contents were fabricated by cold pressing and sintering using rGO/Cu composite powders prepared through molecular-level mixing. During the reduction process, Cu ions were in-situ transformed into nano-Cu particles embedded within the rGO interlayers or anchored onto the rGO surface. The embedded nano-Cu particles enlarged the graphene interlayer spacing, suppressed agglomeration, and strengthened the rGO/Cu interface, while the anchored nano-Cu particles promoted Cu–Cu metallurgical bonding and improved densification during sintering. The results show that CCu1 exhibited the optimum electrical conductivity of 95.10% IACS and a thermal conductivity of 327 W·m−1·K−1, corresponding to increases of 21.4% and 14.7%, respectively, compared with the pure Cu counterpart prepared under identical processing conditions. These improvements arise from the combined effects of enhanced densification and interfacial regulation induced by the embedded–anchored rGO/Cu architecture. The highest compressive strength of 280.2 MPa was achieved at 0.3 wt% GO, while the average friction coefficient decreased from 0.111 to 0.055. These results demonstrate that the interfacial structure between Cu particles can be effectively regulated through the design of rGO/Cu composite powders under cold pressing–sintering conditions. Without relying on SPS or other high-energy sintering techniques, the densification behavior, electrical and thermal transport, mechanical strength, and tribological performance of Cu matrix composites can be simultaneously improved, thereby providing a new strategy for the facile and scalable fabrication of high-performance Cu matrix composites.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Yaoyu Zhang,Yuxiong Wang,Yue Liu,Huimin Xu,Zhongbiao Wu
Pt@Cu-ZSM-5@CuO x catalyst was constructed for the catalytic oxidation of acetonitrile (AN), which achieved a complete mineralization rate and more than 95 % N 2 selectivity within 300–450 °C. Characterization results revealed that the satisfactory synergistic action of hydrolysis and oxidation pathways was well achieved. The NO x release from CN oxidation reaction on out-layer CuO x species and NH x species over-oxidation over Pt sites could be eliminated by NH 3 from CN hydrolysis reaction on Cu ions via internal selective catalytic reduction mechanism. The deep oxidation of carbon-containing intermediates (such as CO etc.) during CN decomposition over Cu species effectively occurred over Pt site. The encapsulation of Pt inner ZSM-5 zeolite not only strengthened low-temperature mineralization rate compared to Cu/ZSM-5 sample, but also inhibited NO x release caused by over-oxidation of AN at an elevated temperature with co-impregnation of Pt species over Cu/ZSM-5. This work provided a viable strategy for designing catalysts to effective abatement of NVOCs.
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Catalysis Science & Technology
·
2022
·Vol. 12
·期 19
·5879-5890
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IF 6.177
Dengfeng Dai,Chao Feng,Minmin Wang,Qingzhou Du,Dandan Liu,Yuan Pan,Yunqi Liu
Biomass-based chemicals as a renewable alternative to petroleum-based chemicals are of great significance. The conversion of biomass-based furfuryl alcohol to pentanediol, including 1,5-pentanediol and 1,2-pentanediol, is explored over a series of bifunctional Cu/MFI catalysts in a continuous-flow reactor. These catalysts are synthesized by supporting copper nanoparticles on MFI zeolites with varying molar ratios of SiO2/Al2O3. Among them, the Z60-10Cu catalyst containing balanced Cu0–Cu+ and Brønsted acid sites exhibits excellent performance, and a high furfuryl alcohol conversion of 99.5% and selectivity of 85.2% for 1,5-pentanediol (69.2%) and 1,2-pentanediol (16.0%) could be achieved (hydrogen pressure: 2.5 MPa) at 160 °C. The experimental results and the results obtained using the DFT technique revealed that the high catalytic activity realized during the processes of ring-opening and hydrogenation could be attributed to the synergistic effect between the Cu species and Brønsted acid sites. The Brønsted acid sites on the Si(OH)Al groups significantly affect the ring-opening process of furfuryl alcohol. The methoxy group on furfuryl alcohol adsorbs on the Cu+ sites, and the hydrogenation saturation of the ring-opening intermediate is realized under the influence of the activated hydrogen units on the Cu0 sites. The results reported herein could help promote the continuous production of high value-added pentanediol from biomass-based raw materials in the presence of non-noble metal catalysts. An economical and feasible path for the transformation of biomass resources into high value-added fine chemicals could also be developed.
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JOURNAL OF HAZARDOUS MATERIALS
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2026
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IF 10.6
Dingqiang Zhang,Xiaoqun Wu,Tengchao Jiao,Weizhen Zhang,Jiahao He,Yanhua Xie,Yingming Hu,Yao Wei
Trace-Cu(II)/CaO 2 /PAC achieves > 95% algal removal in natural waters. • Pre-oxidation degrades algal extracellular matter to aid coagulation. • PAC mitigates matrix interference, indirectly maintaining oxidation. • Intracellular ROS induces functional death without severe lysis. Harmful algal blooms release microcystins and other metabolites that threaten aquatic ecosystems and human health. Conventional removal methods often induce cell lysis and are affected by matrix interference in natural waters, limiting their practical applicability. A sequential process coupling trace-Cu(II)/CaO 2 pre-oxidation with PAC coagulation was developed for efficient algal removal. The system removed 98.5% of M. aeruginosa from lake water. During the 10-min pre-oxidation stage, trace-Cu(II)/CaO 2 effectively degraded extracellular microcystin-LR (MC-LR) and the dissolved organic matter (DOM) surrounding algal cells, thereby weakening electrostatic repulsion and enhancing coagulation efficiency. The coupled process generated Cu(III), •OH, •O 2 − , and 1 O 2 within the cells, which led to functional cell death without severe membrane rupture. Conventional molecular dynamics (MD) simulations confirmed the stability of a representative pentameric cation-channel model, and steered molecular dynamics (SMD) further showed that Cu 2+ and H 2 O 2 could be guided through its pore under an applied axial bias, supporting the physical plausibility of channel-mediated intracellular access. Mechanistically, OH − generated during CaO 2 hydrolysis promoted the Cu(II)/Cu(I)/Cu(III) catalytic cycle and sustained reactive species production, with Cu(III) as the dominant contributor to functional inactivation (68.5%). These findings establish an innovative and practical strategy for the safe and effective removal of algae from contaminated natural waters. Download: Download high-res image (297KB) Download: Download full-size image
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高影响因子
Nanoscale
·
2018
·Vol. 10
·期 37
·17647-17655
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IF 7.233
Ke Yang,Yu Yan,Haiyang Wang,Zhixuan Sun,Wen Chen,Hongtao Kang,Yi Han,Wenquan Zahng,Xiaohua Sun,Zhenxing Li
A novel copper/copper(I) oxide@carbon (Cu/Cu2O@C) core–shell nanocomposite monodispersed on the surface of reduced graphene oxide (defined as Cu/Cu2O@C-rGO) was synthesized using a one-step calcination of Cu-based metal organic frameworks (MOFs)/graphene oxide (GO) composite structure. The size of the resultant Cu/Cu2O@C core–shell nanoparticles (NPs) on the rGO layers were mainly distributed in range of about 90–100 nm with good dispersion, which was characterized using transmission electron microscopy. X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, nitrogen adsorption–desorption isotherms, X-ray photoelectron spectrometry and thermogravimetric analyses were also carried out to characterize the structure and composition of the Cu/Cu2O@C-rGO. The catalytic performance of the Cu/Cu2O@C-rGO composite was evaluated using a reduction reaction from 4-nitrophenol to 4-aminophenol. It was demonstrated that the Cu/Cu2O@C-rGO composite exhibited an excellent catalytic performance, which can reach a nearly 100% conversion rate in 90 s with 0.1 mg of catalyst. This catalyst also showed a good performance for the degradation of other organic dyes such as methylene blue, methyl orange and rhodamine B. Additionally, the core–shell structure exhibited good stability and reusability for the reduction reaction, which was because of its relatively better oxidation resistance than that of the bare Cu NPs. This research provided an efficient and stable non-noble metal-based catalyst derived from the MOF/GO structure.
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PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Fuxia Huang,Zihao Jiao,Feng Wang,Ya Liu,Liejin Guo
Direct photocatalytic CO 2 conversion to C 2 products holds notable potential, but this technology is still limited by the high thermodynamic energy and sluggish kinetics. By introducing Cu in In 4 SnS 8 catalyst, we here developed low S vacancies and chemical reactive sites photocatalysts Cu-In 4 SnS 8 , enabling photocatalytic CO 2 to ethanol with full selectivity. Minor electron paramagnetic resonance peak intensity and large formation energy for S-vacancy suggest Cu introduction suppresses S vacancies formation. Low S vacancies photocatalysts Cu-In 4 SnS 8 possess excellent carrier transfer and separation ability by the steady photoluminescence and transient fluorescence characteristic results. Furthermore, in situ, FTIR measurements confirmed ethanol formation via the presence of the intermediates *COOH, *CO, *OCCO(H), and *OCH 2 CH 3 . Also, theory calculations reveal that Cu efficiently reduces the energy barriers of the rate-limiting steps of *COOH and *COH, and promotes C-C coupling and multi-proton coupled electron transfer processes by co-adsorption and asymmetric charge distribution effects. As a result, the optimized sample achieves 0.73 μmol h −1 CH 3 CH 2 OH generation with full selectivity.
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高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
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IF 8.1
Lu Li,Shiyu Ma,Huimin Liu,Zixuan Zeng,Qijie Li,Chunlin Song,Jingang Yang
Ammonia borane (NH 3 BH 3 ) as a solid chemical hydrogen storage material with a high hydrogen content can be hydrolyzed under mild conditions to release hydrogen. In this work, Fe–Ni–B/Cu(OH) 2 –Cu foam was synthesized by combining in situ growth and electroless plating. Compared with the binary Fe–B/Cu(OH) 2 –Cu foam and Ni–B/Cu(OH) 2 –Cu foam prepared by the same method, the ternary Fe–Ni–B/Cu(OH) 2 –Cu foam has superior catalytic performance. The Fe–Ni–B/Cu(OH) 2 –Cu foam catalyst was able to achieve a maximum hydrogen production rate of 5.6 ml min −1 cm −2 at 298 K with an activation energy as low as 46.3 kJ mol −1 . And more importantly, its catalytic efficiency has hardly decayed after ten cycles. These excellent properties are due to its low activation energy and the large specific surface, multi–site Cu(OH) 2 –Cu–foam carrier.
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Xuli Hu,Zhen Zhang,Zhenyao Li,Yushan Wu,Wei Wei,Yao Wang,Junchen Xu,Mingyue Ding
Regulating oxidation state of Cu-based chalcogenides catalysts during electrolysis is of great significance for efficient CO 2 electrochemical reduction reaction (CO 2 RR) to methanol, which still remains a dramatic challenge. Herein, we construct a heterogeneous Cu 3 VS 4 /CuS electrocatalyst (denoted as CuV x S), in which the in-situ growing Cu-S-V bonds avoid the accumulated electrons on oxidized Cu sites and inhibit the deep reduction of CuS to metallic Cu during electrolysis, maintaining stable and abundant reactive Cu + /Cu 2+ species to promote CO 2 RR performance to methanol. By this design, the CuV 0.1 S catalyst achieves an ultrahigh methanol selectivity of 79.8 %. In-situ FTIR measurement reveals that the synergistic effect of Cu + /Cu 2+ species and Cu-S-V bonding facilitates the *CO adsorption and the subsequent *CO hydrogenation process, which improve the generation of *CHO and *OCH 3 intermediates for enhanced methanol selectivity. This work provides a new insight into stabilizing high oxidation state of Cu-based electrocatalyst to maintain sufficient active sites for CO 2 RR.
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