ChemistrySelect
·
2026
·Vol. 11
·期 20
·e73532
·
IF 2.3
Siyu Mao,Yaqi Fu,Jiaxing Wei,Yichuan Wang,Wei Feng
Manganese superoxide dismutase (SOD) catalyzes the decomposition of hydrogen peroxide (H 2 O 2 ) to generate hydroxyl radicals (•OH). In this study, SOD was encapsulated via coordination with Cu(II), Fe(II), and phosphate in phosphate-buffered saline (PBS) to form a hybrid material denoted as SOD@Cu&Fe&PO 4 . Our study demonstrates that SOD and the coordinated Cu(II)/Fe(II) ions exert a synergistic catalytic effect on •OH generation during H 2 O 2 decomposition. This synergistic behavior stems from the dynamic interplay between the production and consumption of superoxide anion radicals (O 2 •− ). Specifically, O 2 •− is generated as an intermediate in the reactions of coordinated Cu(II) and Fe(II) with H 2 O 2 . The in situ generated O 2 •− is subsequently utilized by encapsulated SOD, which in turn reduces Mn 3 + at the enzyme's active site to Mn 2 + . A continuous supply of O 2 •− to SOD accelerates the Mn 3 + /Mn 2 + redox cycle at its active center. Concurrently, the timely removal of O 2 •− from the Cu(II)/Fe(II)–H 2 O 2 reaction system eliminates the potential inhibition of O 2 •− accumulation, thereby promoting the Fe(III)/Fe(II) and Cu(II)/Cu(I) redox cycles. As a result, SOD@Cu&Fe&PO 4 affords a significantly enhanced •OH generation capacity. Moreover, this hybrid material exhibits enhanced contaminant degradation efficiency and potent antibacterial activity against multidrug-resistant Escherichia coli (MDR E. coli ) and methicillin-resistant Staphylococcus aureus (MRSA). Graphical O 2 •− is generated as an intermediate in the reactions of coordinated Cu(II) and Fe(II) with H 2 O 2 . The in situ generated O 2 •− is subsequently utilized by encapsulated SOD, which in turn reduces Mn 3 + at the enzyme's active site to Mn 2 + . A continuous supply of O 2 •− to SOD accelerates the Mn 3 + /Mn 2 + redox cycle at its active center.
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INORGANIC CHEMISTRY
·
2026
·
IF 4.6
Xi-Ting Zhang,Li-Ping Zhang,Zhong-Lei Xing,Tianze Zhou,Shao-Min Wang,Qing-Yuan Yang
The coordination geometry of metal nodes is a critical yet overlooked variable in metal–organic framework (MOF) design. Here, we show that an amino substituent on the isonicotinic acid linker switches Cu(II) from five-coordinate square-pyramidal to four-coordinate square-planar, collapsing the framework from a 3D microporous network (Cu-ina, ina = isonicotinic acid) to a 2D layered structure (Cu-2ain, 2ain = 2-aminoisonicotinic acid). The amino group strengthens the Cu–N bond and eliminates one Cu–O contact, reducing the pore-limiting diameter to 3.27 Å and imposing complete size exclusion of both CHF3 (∼4.6 Å) and N2 (3.64 Å) in Cu-2ain. The 3D framework Cu-ina, free of this modification, achieves a CHF3 uptake of 50.1 cm3 g–1 at 298 K with an IAST selectivity of 46 for CHF3/N2, driven by cooperative C–H···F and C–H···O hydrogen bonding confirmed by GCMC simulations and DFT calculations. Five-cycle breakthrough experiments confirm excellent regenerability. This work demonstrates that ligand functionalization can inadvertently restructure metal coordination geometry and collapse framework dimensionality, overriding any intended surface-chemical benefit.
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PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2026
·
IF 9.1
Xin Zhou,Wei Li,Jian Zhang,Ningruo Wang,Yizhou Tu,Yang Li,Yue Yuan,Ningjie Fang,Chuanshu He,Yang Liu
The complete dehalogenation and mineralization of halogenated organic pollutants have consistently posed a significant technical challenge in detoxification processes. The redox synergistic system effectively reduces the production of highly toxic, small molecular halogenated hydrocarbons during mineralization. The synergistic activation of sulfites by zero-valent iron‑copper materials enables rapid removal of efficiently eliminate florfenicol (FF), however, a comprehensive understanding of the mechanism is lacking. Here, we employed experimental data and density functional theory calculations to demonstrate that the synergistic degradation of FF is an interdependent and interconnected process. Specifically, the reduction process primarily follows the sequence of chlorine removal followed by fluorine removal, while the oxidation process primarily involves three key reaction sites at C11, C17, and C20, where hydroxyl substitution reactions occur. Notably, the dehalogenation process reduces the activation energy required for oxidation. The activation energy for the oxidation reaction at the C17 position is 6.34 kcal/mol, whereas after dehalogenation, it decreases to 5.84 kcal/mol at the same site. Oxidation also affects the distribution of internal charge density within the molecule, thereby influencing the dehalogenation reaction. Furthermore, both toxicity predictions and experimental results indicate that the substances produced by synergistic degradation exhibit significantly lower toxicity than those generated by oxidation alone. The degradation mechanism of FF by the redox synergistic system provides valuable insights into the detoxification of halogenated organic compounds.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2026
·
IF 8.7
Zhu Xiong,Huisheng Huang,Fenggui Chen,Shuying Kong,Fulan Zhang
Transforming agricultural waste into functional catalysts addresses both environmental and resource challenges. Specifically, cellulose from discarded carmine radish residue (CRC) was made into a porous support for copper nanoparticles (Cu NPs). Inherent brittleness limits cellulose-based materials' practical use, so hexamethylene diisocyanate (HDI) was introduced as a covalent crosslinker. This approach replaces partial interchain hydrogen bonds with urethane linkages, building a resilient three-dimensional (3D) network in the CRC matrix. FTIR, XRD and 2D-WAXS verified the crosslinking, while low-field NMR showed the chemical network accounted for roughly 66.77% of the system. Mechanical properties were notably enhanced: compressive modulus rose from 30 kPa to 130 kPa, compressive strength stayed at 80 kPa, and compressive strain increased from approximately 62% to 81%. Molecular dynamics simulations confirmed cohesive energy dropped from 101.83 kJ mol −1 to 56.27 kJ mol −1 , explaining improved energy dissipation. The toughened CRC scaffold was loaded with ∼35 nm Cu NPs to form a CRC/nano-Cu composite. When applied to catalytic dye degradation using NaBH 4 , the composite achieved near-complete degradation of methylene blue (MB) within 25 min. This performance dramatically outperforms the non-catalytic reaction, which only achieved 29% degradation after 240 min. Furthermore, electrostatic interactions driven by the electron-rich Cu surface conferred strong charge-selectivity for cationic dyes, while the composite retained robust reusability over 5 cycles and high activity under severe ionic interference. This work offers a novel strategy for high-value biomass waste utilization and a mechanism for designing strong bio-based catalytic materials by enhancing energy dissipation through covalent crosslinking.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Guo Yu Yong,Lin Zhu Dai,Wan Ni Gan,Chen Yu Yang,Ting Li,Ying Ying Yang,Hao Jie Geng,Hong Qun Luo,Nian Bing Li
Sub-nanometer Cu are clusters are anchored on Ni-MOF offer abundant active sites. • Cu@Ni-MOF acts as a highly efficient tandem electrocatalyst for NO 3 ¯ reduction. • DFT calculations confirm the *H adsorption energy difference on Cu versus Ni sites. • Ni–O–Cu bridges enable reverse *H spillover from the Ni-MOF to Cu sites. Electrocatalytic nitrate reduction (NO 3 − RR) to ammonia offers a sustainable strategy for wastewater treatment and the balance of the nitrogen cycle. However, this process has long faced challenges from competing side reactions, low selectivity, and sluggish hydrogenation kinetics. Herein, we present a Cu@Ni-MOF catalyst, fabricated by anchoring Cu sub-nanoclusters onto a nickel-metal-organic framework (Ni-MOF) support, which demonstrates exceptional performance for NO 3 − RR. The catalyst achieves a peak NH 4 + Faradaic efficiency (FE) of 96.8% with a production rate of 0.44 mmol h −1 cm −2 and minimal NO 2 − accumulation, and near-total FE (∼100%), which indicates high selectivity and minimal side products. Integrating electrochemical analysis with theoretical calculations establishes a cooperative tandem mechanism: the Cu sites promote NO 3 − adsorption and conversion to NO 2 − , while the Ni-MOF efficiently dissociates water to generate hydrogen species (*H), which migrate via reverse hydrogen spillover through Ni − O − Cu bridges to facilitate further hydrogenation of NO 2 − intermediates on Cu sites. This synergistic process enhances intermediate conversion and overall catalytic efficiency, providing a promising strategy for sustainable electrocatalytic ammonia synthesis. Download: Download high-res image (155KB) Download: Download full-size image
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Journal of Environmental Chemical Engineering
·
2025
·
IF 7.2
Xinyue Liang,Weihong Zhang,Xiaolong Yao,Zhengyang Feng,Qingwei Bu,Wenwen Gong,Wei Wang,Chun Wang,Yingxue Sun
Adsorption-electrocatalytic oxidation is a promising technology for organochlorine removal; however, its practical application is hindered by electrode limitations in activity, stability, and mechanistic understanding. In this study, a copper-doped ZIF-8/multi-walled carbon nanotube composite electrode (Cu-ZIF-8/MWCNTs/CC) was innovatively designed. Adsorption-electrochemical batch experiments were conducted to systematically investigate the degradation behaviors of three typical organochlorine contaminants: 2,4-dichlorophenol (2,4-DCP), triclosan (TCS), and chloramphenicol (CAP), using MOF-based electrodes. The results demonstrate that compared to the undoped ZIF-8/MWCNTs/CC, the incorporation of Cu introduced additional mesoporous structures and Cu-N coordination bonds, which effectively enhanced adsorption performance based on the size-matching effect and d-band center theory. Furthermore, the highly reversible and kinetically rapid Cu 2 + /Cu + redox couple served as an efficient mediator for charge transfer, thus promoting the synergistic adsorption and electrochemical degradation of organochlorine contaminants. Notably, the material maintained considerable removal efficiency even under competitive conditions in multicomponent systems. Mechanistic investigation demonstrated that hydroxyl radicals (·OH) preferentially attacked critical chemical bonds (including C-Cl, ether, and amino groups) in accordance with density functional theory (DFT) predictions. This reaction pathway resulted in the generation of less toxic intermediates that were eventually mineralized into CO 2 and H 2 O. The ecological structure-activity relationships (ECOSAR) model further confirmed the low acute and chronic toxicity of the major degradation products. Moreover, the electrode maintained high removal efficiency across multiple consecutive cycles, demonstrating excellent stability and reusability. Collectively, this work proposes a novel strategy for the synergistic adsorption and electrocatalytic removal of organochlorine contaminants; thereby highlighting its significant potential for practical application.
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ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Junfang Ding,Changjin Xu,Xinyi Yao,Kunming Hou,Yinkang Yang,Dan He,Hao Chai,Xiaomin Sun,Shanghong Zeng
The development of ultrafine metal oxide nanoparticles anchored on reducible oxide supports with precisely engineered interfacial active sites has emerged as a critical frontier in heterogeneous catalysis. However, conventional synthesis strategies struggle to reconcile high loading with ultrafine dispersion, often leading to nanoparticle aggregation and compromised stability. Herein, we present a coordination chemistry-driven strategy integrating the hard–soft acid–base principle with a water-etching process to synthesize ultrafine CuOx nanoparticles anchored on CeO2. By exploiting the differential coordination affinities of Ce3+ and Cu2+ with carboxyl ligands in a bimetallic BTC precursor, selective segregation during solvothermal synthesis was achieved. Ce3+ formed a stable framework with carboxyl groups, while Cu2+ underwent a hydrolysis-induced migration to surface defect sites. Regulating the Cu2+/Ce3+ ratio enabled precise control over CuOx dispersion, interfacial Cu–O–Ce bonding, and local structure. The optimized catalyst exhibited a remarkable Cu loading of 21.94% with high dispersion, lattice distortion, and enhanced metal–support interactions. Notably, the designed catalyst demonstrated exceptional stability under H2-rich streams, which achieved a CO conversion enhancement from 67.4 to 77.7% over 40 h through the interfacial stabilization of metastable Cu+-Ov-Ce4+ active configurations. Advanced characterization and density functional theory (DFT) calculations revealed that the enhanced interfacial Cu–O–Ce interactions and unsaturated coordinated CuOx species facilitated electron transfer, oxygen activation, and CO adsorption, synergistically boosting the catalytic performance via the Mars–van Krevelen mechanism. This work establishes a rational coordination chemistry-guided paradigm for designing high-performance catalysts with precisely engineered active sites.
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PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Lingwu Meng,Maosheng Lin,Qirui Guo,Longzhao Zhang,Xiangyu Huang,Chenrao Hu,Shule Zhang,Weihua Ma
A novel Cu@SZN-2Si catalyst with both microporous and mesoporous structures was successfully fabricated using a new template agent (BCph-10-6-6). This catalyst showed outstanding catalytic performance in the selective catalytic oxidation (SCO) of triethylamine (TEA). Notably, in contrast to the conventional mesoporous Cu@SZ-2Si_CTAB synthesised with CTAB, Cu@SZN-2Si presented a flower-like nanosheet morphology. It boasted a higher density of Lewis acid sites and more surface-adsorbed oxygen (O ads ). Under the reaction conditions at 280 °C, the TEA conversion reached 100 %, and the N 2 yield was as high as 99.2 %. Moreover, in the presence of 10.0 vol% H 2 O vapour, the catalytic activity of Cu@SZN-2Si remained above 87.3 % at 280 °C and maintained stable operation for 130 h at 400 °C. Structural analysis coupled with DFT calculations revealed that Si incorporation enabled the crystallization of tetragonal ZrO 2 in the presence of SO 4 2− ions, while forming an amorphous SiO 2 that encapsulated the ZrO 2 surface. This structural characteristic significantly increased the number of isolated Cu 2+ species and acidic sites on the catalyst surface. The strong interaction between these isolated Cu 2+ species and acidic sites was crucial for promoting the adsorption and activation of TEA. In addition, in-situ DRIFTs results indicated that TEA first adsorbed on the Cu@SZN-2Si surface, followed by a thermal decomposition process. The cleavage of the C-N bond in TEA generated NH* intermediates, which were essential for N 2 generation and promoted the SCO of TEA.
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JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Tenglong Jin,Hongyan Zhuo,Linlin Feng,Zhen Fu,Miao Wang,Dongyang Xie,Wenmiao Chen,Yanli Chen
Efficient and low-cost electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial for the development of zinc-air batteries (ZABs). In this study, we designed a Core-shell hollow zeolitic imidazolate framework (ZIF) material Cu-ZIF-67/ZIF-8 with Cu-doped ZIF-67 (Cu-ZIF-67) core and a ZIF-8 shell. The hollow structure (ZIF-67/ZIF-8-h) was constructed via solvent-assisted phase transformation. The hollow structure, characterized by hierarchical porosity, not only facilitated mass transfer but also served as a prerequisite for Cu SAC formation, leading to coexisting of Cu single atoms (Cu SAC) and Co nanoparticles (Co NPs) after pyrolysis. Cu SAC modulated the d-band center of Co NPs, optimizing the adsorption of oxygen-containing intermediates. In alkaline media, Cu-Co/CN-h exhibited excellent bifunctional catalytic activity, with an ORR half-wave potential of 0.93 V and an OER overpotential of 338 mV at 10 mA cm −2 . When used as the cathode in a flexible ZABs, Cu-Co/CN-h demonstrated a high peak power density of 108 mW cm −2 and outstanding durability over 60 h. This work innovatively provides a strategy for break traditional scaling relationships with hierarchal porosity and synergistic Cu-Co sites.
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Food and Bioprocess Technology
·
2026
·Vol. 19
·期 3
·152
·
IF 5.6
Yang Lingfan,Liu Ruiqi,Shi Yingkun,Li Changhao,Wang Guangxian,Xie Haijiao,Luo Ruiming,Wang Songlei
Xanthine (XA) and hypoxanthine (HA) are key biochemical markers of meat freshness, yet rapid, wide-range, and enzyme-free quantification in complex meat matrices remains challenging. Here we report a density functional theory (DFT)-guided Cu–MoS 2 /g-C 3 N 4 heterostructure electrochemical sensor for broad-range non-enzymatic detection of XA and HA. The heterojunction prepared via a hydrothermal and ultrasonic strategy provides an efficient charge-transport pathway and enriched catalytic interfaces. DFT calculations reveal pronounced interfacial charge redistribution and strong adsorption of XA and HA on the Cu–MoS 2 /g-C 3 N 4 surface, with adsorption energies of − 0.98 eV for XA and − 2.16 eV for HA, explaining the boosted electrooxidation response. The sensor achieves low detection limits of 0.15 μM for XA and 0.28 μM for HA and wide linear ranges from 0.913 to 1643.5 μM and from 0.918 to 1653.1 μM, respectively, and enables simultaneous quantification from 0.5 to 400 μM with excellent linearity. Good stability, reproducibility, and anti-interference capability are obtained. In real meat samples, recoveries from 90.7% to 108.3% for XA and from 91.3% to 111.4% for HA agree well with high-performance liquid chromatography, supporting rapid meat freshness evaluation.
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CERAMICS INTERNATIONAL
·
2026
·
IF 6
Wang-Zhi Xu,Hai-Sheng Gong,Min-Hui Wang,Di Zhang,Jian Sun,You-Jun Lu,Lai-Ma Luo
To develop high-performance W–Cu conductor pastes for high-temperature co-fired ceramics (HTCC), graded particle-size design and ball-milling modification were systematically investigated. The particle-size distribution and powder morphology were changed, resulting in pastes with improved rheological stability and electrical conductivity. Rheological analysis combined with microstructural characterization revealed that powder size and morphology jointly controlled rheological behavior, sintering densification, and electrical conductivity. The optimized pastes exhibited improved flowability and dense sintered films. Electrical testing showed that resistivity decreased significantly, from 57.77 ± 2.41 mΩ·cm for coarse mixed powders to 5.80 ± 0.37 mΩ·cm for ball-milled powder s. Inspired by previous studies on W–Cu bulk composites, ball milling was employed to induce lamellar particle morphologies, which facilitated interparticle contact, promoted the formation of conductive networks. As a result, dense W–Cu films with reduced resistivity were successfully fabricated, demonstrating the feasibility of W–Cu pastes as advanced metallization materials for HTCC.
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CHEMICAL ENGINEERING JOURNAL
·
2026
·
IF 13.2
Shibo Zhao,Yanping Cui,Qiao Huang,Xian Xiang,Yuqing Qu,Chu Xiong,Bolin Li,Caixia Wen
The pervasive and highly stable organophosphate, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) in electroplating wastewater poses a significant challenge to conventional treatment due to its recalcitrant nature. Herein, we report a novel, solar-driven electro-Fenton (EF) system for the efficient degradation of HEDP and simultaneous recovery of phosphorus. This system uniquely features an apricot shell biochar-modified graphite felt (BCGF) cathode, which facilitates in-situ H 2 O 2 generation. Crucially, the process synergistically activates trace endogenous Cu(II) (0.02 mmol/L) within the wastewater, promoting the generation of the highly potent oxidant, Cu(III), for HEDP degradation. Under optimized conditions (50 °C), the system achieved 97.6% HEDP removal within 60 min. Mechanistic investigations revealed that elevated temperatures (from 10 °C to 50 °C) accelerated the Cu(I)/Cu(III) redox cycle, further enhancing degradation efficiency. The BCGF cathode exhibited exceptional stability, maintaining high performance over 30 consecutive cycles. Entirely driven by solar energy, the system achieved over 94% HEDP removal in 60 min, presenting a sustainable and cost-effective strategy for treating persistent organophosphorus pollutants and valorizing waste resources. Solar-Driven Cu(II)/BCGF system also demonstrated excellent performance in treating complex simulated electroplating wastewater, achieving an 84.7% degradation rate of 1761 mg/L (8.55 mmol/L) HEDP within 7 h.
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