Journal of Environmental Sciences
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2026
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IF 6.5
Jiaqi Ding,Xiaolin Xiong,Huanhuan Shi,Yuxiao Mu,Haojun Ji,Jingwen Wang
pH switches reactive species in ZVC/PAA: HO • at pH 3, Cu(III) at pH 7. • Surface Cu x O shell is the key site governing the generation of reactive species. • HO • -dominated system rapidly removes diverse sulfonamides with non-selectivity. • Cu(III) system selectively degrades sulfonamides containing heterocyclic rings. • ZVC demonstrates higher reusability and lower Cu ions leaching at pH 7. Zerovalent copper (ZVC) has garnered considerable attention in Fenton-like reactions, but the surface properties of ZVC that regulate reactive species (RSs) generation remain elusive. Herein, we systematically investigated the pH-dependent regulation of hydroxyl radical (HO • ) and high-valent copper (Cu(III)) generation during peracetic acid (PAA) activation by ZVC for the degradation of sulfonamide antibiotics (SAs). Characterization results revealed that ZVC has a core-shell structure, in which the surface copper oxide (Cu x O) layer serves as the primary active site. Theoretical and experimental analyses elucidated that pH modulates the surface properties of ZVC. At pH 3, the protonation of Cu x O promotes the generation of HO • in the ZVC/PAA system; conversely, under neutral conditions (pH 7.0), the unprotonated state favors the formation of Cu(III) as the dominant RSs. This trade-off between HO • and Cu(III) generation leads to distinct degradation performance for SAs degradation. HO • -dominated system achieved non-selective removal (>96 %) of various SAs; whereas the Cu(III) pathway selectively degraded SAs with heterocyclic rings at pH 7. The Cu(III) pathway outperformed the HO • system in terms of humic acid tolerance and catalyst recyclability in the ZVC/PAA process. This work clarifies the decisive role of surface protonation of ZVC in steering HO • versus Cu(III) pathways and provides a theoretical basis for designing pH‑specific Fenton-like reaction processes. Download: Download high-res image (355KB) Download: Download full-size image
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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
Chen Wang,Congbi Li,Xiaohui Wu,Xiangling Zhang,Mingjie Huang,Tao Zhou
Efficient and sustainable generation of high-valent metal-oxo species (HVMs) is critical for selective decontamination via Fenton-like catalysis, however, maintaining electron density balance at the active sites remains challenging. In this study, a zeolite-supported CuO catalyst was found to induce complete and selective Cu(III) oxidation of organics through persulfate (PDS) activation. PDS activation and pollutant oxidation occurred simultaneously at the electron-rich ≡Cu sites and electron-deficient ≡Al centers, respectively. Notably, zeolite could successfully serve as an electron buffer by creating dual active centers with distinct electron densities, stabilizing the generation and retention of ≡Cu(III) for exceptional anti-interference capacity. Strong metal-support interactions tuned the ≡Cu d-band center closer to the Fermi level, efficiently promoting electron transfer to ≡Cu sites through the Al/Si-O-Cu bond for the formation of ≡Cu(III). This study unveils a zeolite-based electron buffering strategy and presents an advanced approach for developing highly efficient catalysts in PDS activation and HVMs-mediated water purification.
研究领域:
环境科学
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催化化学
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高影响因子
ADVANCED SYNTHESIS & CATALYSIS
·
2026
·Vol. 368
·期 5
·e70307
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IF 3.7
Wei Rao,Yifan Jiang,Qiong Liu,Junjun Zhang,Die He,Rong Chen
While high-valent copper intermediates are pivotal for efficient peroxydisulfate (PDS) activation, their generation and role in heterogeneous catalysis remain unclear. Herein, we demonstrate that a nonstoichiometric Cu 0.84 Bi 2.08 O 4 catalyst enables the dark activation of PDS via a novel pathway dominated by a surface-bound Cu(III)-peroxo intermediate ( ≡ Cu(III)-O−O−SO 3 ). A suite of spectroscopic and chemical probes revealed that this Cu(III)-peroxo species, along with superoxide radicals (•O 2 − ), acts as the primary oxidant, enabling the highly selective and rapid degradation of bisphenol A (BPA) and other phenolic pollutants. Furthermore, H 2 O 2 generated from PDS hydrolysis synergistically participates in the reaction, accounting for the exceptionally high PDS utilization efficiency of the system. The system exhibits remarkable robustness, maintaining high activity over a wide pH range (4–11) and demonstrating strong resistance to interference from ions. This study elucidates a distinct Cu(III)-peroxo-mediated mechanism and offers a new strategy for designing highly selective catalysts for environmental remediation.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2026
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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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高影响因子
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
Green Energy & Environment
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2020
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IF 6.395
Hongmin Zhang,Qingzhu Jia,Fangyou Yan,Qiang Wang
In this study, a series of CuMgAl layered double oxides (CuMgAl-LDOs) were obtained via calcination of CuMgAl layered double hydroxides (CuMgAl-LDHs) synthesised via a co-precipitation method. The results show that CuMgAl-LDO can be prepared using an optimal Cu : Mg : Al molar ratio of 3 : 3 : 2, NaOH : Na 2 CO 3 molar ratio of 2 : 1, and calcination temperature of 600 °C. CuMgAl-LDO is a characteristic of mesoporous material with a lamellar structure and large specific surface area. The removal efficiency of sulfameter (SMD) based on CuMgAl-LDO/persulfate (PS) can reach > 98% over a wide range of initial SMD concentrations (5–20 mg L −1 ). The best removal efficiency of 99.49% was achieved within 120 min using 10 mg L −1 SMD, 0.3 g L −1 CuMgAl-LDO, and 0.7 mmol L −1 PS. Kinetic analysis showed that the degradation of SMD was in accordance with a quasi-first-order kinetic model. The stability of the CuMgAl-LDO catalyst was verified by the high SMD removal efficiency (> 97% within 120 min) observed after five recycling tests and low copper ion leaching concentration (0.89 mg L −1 ), which is below drinking water quality standard of 1.3 mg L −1 permittable in the U.S. Radical scavenging experiments suggest that SO 4 · − is the primary active species participating in the CuMgAl-LDO/PS system. Moreover, our mechanistic investigations based on the radical scavenging tests and X-ray photoelectron spectroscopy (XPS) results indicate that Cu (II) –Cu (III) –Cu (II) circulation is responsible for activating PS in the degradation of SMD and the degradation pathway for SMD was deduced. Accordingly, the results presented in this work demonstrate that CuMgAl-LDO may be an efficient and stable catalyst for the activation of PS during the degradation of organic pollutants.
研究领域:
环境科学
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催化
·
水处理
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高影响因子
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