JOURNAL OF CATALYSIS
·
2025
·
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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MICROPOROUS AND MESOPOROUS MATERIALS
·
2025
·
IF 4.7
Jiaze Chen,Huijie Xie,Yusen Chen,Dong Guo,Binjie Li,Xuanxuan Sun,Volodymyr Turkevych,Caixia Li,Dehong Chen,Lei Wang,Bin Li
Fenton-like degradation based on iron catalyst have been developed to remove organic pollutants from wastewater. However, iron-based catalysts still face challenges of poor accessibility and stability of active sites. Here, we report a facile and green method for the preparation of Fe x Cu (1-x) @HZSM-5 catalyst using ethylenediamine as an organic ligand to stabilize metal species via a combination of solid-state grinding and steam-assisted crystallization methods without organic templates. Due to the confinement of zeolite ZSM-5 framework and synergistic effect of Fe and Cu bimetals, the optimized Fe 0.8 Cu 0.2 @HZSM-5 catalyst exhibits excellent activity and reusability in the Fenton-like degradation of methylene blue at the neutral condition. Our strategy for fabricating bimetal@zeolite can bring about new thoughts for the preparation of iron-based catalyst with high efficiency for Fenton-like degradation.
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BIOMASS & BIOENERGY
·
2025
·
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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INORGANIC CHEMISTRY COMMUNICATIONS
·
2025
·
IF 5.4
Jingrui Hu,Zaihua Duan,Chong Tan,Yi Wang,Zhen Yuan,Yadong Jiang,Huiling Tai
Recently, the self-powered electrochemical humidity (ECH) sensors have received extensive attention. In this work, a self-powered ECH sensor is constructed based on cellulose nanocrystals (CNC)/NaCl humidity sensing material, and Cu and Zn electrodes. The results show that the proposed CNC/NaCl ECH sensor has good humidity sensing and power generation performances. Specifically, it has a wide humidity detection range (10.9 %–91.5 % relative humidity (RH)), fast response/recovery speed (27/22 s), and good linearity (41.1 %–91.5 % RH) at room temperature of 25 °C. A single CNC/NaCl ECH sensor can achieve high response voltage of 0.62 V, large short-circuit current (∼20 μA) and load power (∼4.48 μW) at 91.5 % RH. In addition, this work verifies the potential application of the CNC/NaCl ECH sensor in respiratory rate detection.
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Waste and Biomass Valorization
·
2024
·
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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Engineering
·
2024
·
IF 10.1
Qixiang Duan,Chao Hou,Tielong Han,Yurong Li,Haibin Wang,Xiaoyan Song,Zuoren Nie
Immiscible bimetal systems, of which tungsten–copper (W–Cu) is a typical representative, have crucial applications in fields requiring both mechanical and physical properties. Nevertheless, it is a major challenge to determine how to give full play to the advantages of the two phases of the bimetal and achieve outstanding comprehensive properties. In this study, an ultrafine-grained W–Cu bimetal with spatially connected Cu and specific W islands was fabricated through a designed powder-mixing process and subsequent rapid low-temperature sintering. The prepared bimetal concurrently has a high yield strength, large plastic strain, and high electrical conductivity. The stress distribution and strain response of individual phases in different types of W–Cu bimetals under loading were quantified by means of a simulation. The high yield strength of the reported bimetal results from the microstructure refinement and high contiguity of the grains in the W islands, which enhance the contribution of W to the total plastic deformation of the bimetal. The high electrical conductivity is attributed to the increased mean free path of the Cu and the reduced proportion of phase boundaries due to the specific phase combination of W islands and Cu. This work provides new insight into modulating phase configuration in immiscible metallic composites to achieve high-level multi-objective properties.
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LANGMUIR
·
2024
·
IF 3.7
Wanyi Li,Xu Bai,Jian Liu,Mingjie Chen,Jiamei Hao,Hulin Gao
In this study, pyrite was used as the research object, and the behavior and mechanism of a copper-ion-enhanced organic depressant in depressing pyrite flotation were studied. Microflotation experiments showed that, after the addition of CuSO4 and N,N-dimethyldithiocarbamate (N,N-DDS), the floating collection efficiency of pyrite declined from 82.37 to 21.03% at pH 8.5. Infrared spectroscopy studies indicated that the addition of CuSO4 caused a significant enhancement in the characteristic N,N-DDS peaks on the pyrite surface. X-ray photoelectron spectroscopy (XPS) revealed that, following the addition of CuSO4 and N,N-DDS, the relative atomic concentration of N 1s considerably enhanced on the surface of pyrite, with N 1s derived from N,N-DDS. Time-of-flight secondary ion mass spectrometry showed that, before and after the addition of CuSO4, the normalized peak values of CSN– on the pyrite superficial layer were 0.0116 and 0.0032, respectively. All of the above-mentioned results indicate that the Cu ion promotes the adsorption of N,N-DDS on pyrite and facilitates the formation of complex ((CH3)2NCSS)2Cu. The N and S atoms in −NCS and metal ions formed chemical bonds, which were the primary mechanism of the interaction between N,N-DDS and pyrite. This process reduces the floatability of pyrite and achieves the selective depression of pyrite.
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NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Ziyu Tang,Chuanlin Mou,Yadong Li,Shihao Chen,Xianmin Yang,Xu Ding,Hongbo Deng,Linyuan Wang
Here, we report a controllable strategy for fabricating monodispersed microspheres composed of poly(butyl methacrylate) (BMA) and silane-modified Cu/Ni-embedded metal-organic framework (MOF)-TiO₂ composites (denoted as BMA@Cu/Ni@MOF-TiO₂ microsphere) for efficient photocatalytic degradation. Monodispersed oil-in-water (O/W) emulsion templates are prepared by a microfluidic device, which contain silane-modified Cu/Ni@MOF-TiO2 in oil phase. Utilizing benzildimethyl ketal (BDK) as a photoinitiator, porous microspheres can be obtained through a straightforward photopolymerization process initiated by ultraviolet light. When the concentration of the surfactant polyglycerol polyricinoleate (PGPR 90) is 14% (w/v) and the crosslinker trimethylolpropane trimethacrylate (TMPTMA) is 12% (w/v), the BMA@Cu/Ni@MOF-TiO2 microspheres have good monodispersity, and the average diameter is 180.7 μm and coefficient of variation (CV) is 3.64%. When silane-modified Cu/Ni@MOF-TiO2 loading is 0.4% (w/v), the removal rate to methylene blue (MB) is up to 96.2% in 20 min, which is higher than that of powdered (86.6%). Under the optimal conditions, the removal rate of methylene blue reached 99.3% within 50 minutes. Moreover, after 5 cycles of testing, the degradation efficiency remained above 97.94%,, which strongly demonstrated the reusability of BMA@Cu/Ni@MOF-TiO2 microspheres. The photocatalytic mechanism involves the generation of electron-hole pairs in Cu/Ni@MOF-TiO2 under light irradiation, which react with O2 to produce reactive oxygen species (ROS) to degrad MB. The characterization results of XPS, and FTIR show that the silane-modified Cu/Ni@MOF-TiO2 is successfully loaded into the microspheres. BMA@Cu/Ni@MOF-TiO2 microspheres have a specific surface area of 5.962 m2/g and a specific volume of 2.491 cm3/g, providing sufficient diffusion channels and active sites for MB dyes. Therefore, BMA@Cu/Ni@MOF-TiO2 microspheres have excellent recyclability, high stability and attractive photocatalytic degradation efficiency, and show potential application prospects in the future treatment of dye wastewater.
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iScience
·
2025
·
IF 4.1
Hong Qian,Binxia Yuan,Yuhao Liu,Li Wang,Rui Zhu,Pengyu Dong
TiO 2 has low photocatalytic activity due to its easy recombination of photogenerated charges and low visible light utilization efficiency. This study utilized the keto-enol tautomerism principle of fructose in an alkaline environment to successfully obtain Cu 2 O/TiO 2 (CT), Cu 2 O/TiO 2 /Cu (CTC), and TiO 2 /Cu (TC) catalysts. As Cu(I) transformed into Cu(0), the bandgap narrowed, significantly enhancing visible light absorption. Photocatalytic tests showed that CT-0.15 exhibited the highest hydrogen production rate (279.53 μmol g −1 h −1 ), which was 25.18 times higher than that of TC-2. However, CTC-1 had the highest CO production rate (10.58 μmol g −1 h −1 ). Optoelectronic test revealed that CT-0.15 and CTC-1 had higher separation efficiency of photogenerated exciton. Density functional theory (DFT) calculations indicated that the change in the valence state of Cu influenced the reaction mechanism, with CT being favorable for the adsorption of H + in HER and CTC promoting the adsorption of CO 2 in carbon dioxide reduction reaction (CO2RR).
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JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
·
2025
·
IF 3.1
Li Kaiqian,Zhang Xupeng,Li Xianghong,Chang Qiaowen,Deng Shuduan,Zhu Gang
Introducing novel bimetallic metal–organic frameworks (Cu/Zr-MOF) into wood cellulose scaffolds via an in situ growth strategy represents an effective approach to enhance the fire retardancy of wooden products. This work evaluates the effects of Cu/Zr-MOF loading content embedded in wood composite on the MOF morphology and flame retardancy of natural wood (NW). We discovered that MOF loading has a significant impact on the morphology of Cu/Zr-MOF. Specifically, with an increase in the amount of MOF precursors, the morphological transformation is from spherical to regular octahedra. Furthermore, the incorporation of high MOF loading remarkably enhanced the thermal stability at the early stage and exhibited significantly improved residual content. With 24 mass% loading of Cu/Zr bimetallic MOF, the highly flame-retardant wood composite (Cu-U-W-3) was obtained. Compared to pure NW, the peak heat release rate (pHRR) and total heat release (THR) were reduced to 25.25 W g −1 and 5.0 kJ g −1 , respectively. The limiting oxygen index (LOI) of the treated sample reached 24.81%, showing outstanding self-extinguishing ability. According to the char residue analysis, it was found that Cu-Zr bimetallic MOF anchored on the cell wall exhibited catalytic carbon-forming effect, thereby facilitating the generation of high-quality residual char. The enhanced fire safety of natural wood can be attributed to the oxygen barrier and the reduced heat transfer characteristics of the dense carbon layer. This work presents a novel methodology for the fabrication of bimetallic MOF hybrid flame retardants, with the objective of enhancing the flame retardancy of wooden products.
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Foods
·
2025
·Vol. 14
·期 8
·1311
·
IF 5.1
Yanyan Huang,Jiatong Han,Yi Ping,Xin Chen,Yiming Zhao,Ge Chen,Jun Lv,Donghui Xu,Yanguo Zhang,Jing Chen,Guangyang Liu
In this study, two types of Cu-MOFs (Cu-TCPP and CuO-TCPP) with a two-dimensional layered porous structure were prepared via in situ polymerization using Cu2+, CuO, and TCPP as raw materials. Both Cu-MOFs exhibited peroxidase-like activity, capable of catalyzing the oxidation of TMB by H2O2to form oxTMB, resulting in an absorption peak at 652 nm and a color change from colorless to blue. Subsequently, the addition of AA can reduce oxTMB back to TMB, causing the color of the system to lighten or become colorless. Based on this principle, a simple and rapid colorimetric method for AA detection was established and successfully applied to the detection of TAC in fruits and vegetables. The results showed that Cu-TCPP and CuO-TCPP had a large linear range of ascorbic acid detection of 0.01–100 mM (Cu-TCPP) and 0.05–100 mM (CuO-TCPP). This study not only provides a novel method for preparing nanozymes with peroxidase-like activity, but also offers a simple approach for analyzing the TAC of food.
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Qingyuan Sheng,Yaping Zhang,Xiaofei Zhu,Qiwei Chen,Shangyu Li,Jinghe Bai,Wenfu Yan,Defeng Zhou
Enhancing the oxygen reduction catalytic activity and thermal compatibility of cathode materials under intermediate-temperature conditions remains pivotal for advancing the commercialization of solid oxide fuel cells (SOFCs). Therefore, this article regulates the crystal structure of NdBaCo 2 O 5+δ (NBC)-based double perovskite by Cu, replacing Co with a small amount of Cu ions to increase the oxygen vacancy content of the cathode material and reduce the thermal expansion coefficient (TEC) of NBC-based materials, to improve the electric catalytic activity and long-term stability of SOFC. The distribution of relaxation time results confirms that compared with NBC, NdBaCo 1.8 Cu 0.2 O 5+δ (NBCC2) can greatly enhance oxygen's dissociation and adsorption rates. As a symmetrical cell at 650 °C, the area-specific resistance (ASR) of NBCC2 is only 0.067 Ω cm −2 , which is about 40 % of NBC. As the cathode of SOFC, the maximum power density of the NBCC2-based cell reaches 0.67 W cm 2 , which is 1.58 times that of NBC, and Cu doping improves the long-term stability problem caused by the high TEC of Co-based materials. This study provides an effective solution for further enhancing the electrocatalytic activity of Co-based perovskite and addressing stability issues caused by high TEC.
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