Nature Communications
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2025
·Vol. 16
·期 1
·1-12
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IF 15.7
Zhang Tianyu,Wang Weibo,Liu Wenxian,Guo Zhengxiao,Liu Junfeng
Reconstruction of metal-organic frameworks often occurs under reaction conditions, thereby impeding true active species identification and hindering mechanism understanding. Herein, we present the mechanistic insight underlying the electrochemical synthesis of deprotonated anion of H 2 O 2 (HO 2 − ) via 2e − oxygen reduction by ultrathin Ni-benzenedicarboxylic acid (NiBDC), guided by its thickness-dependent performance and pH-induced reconstruction behavior. The real active species are identified as alkaline-reconstructed β-Ni(OH) 2 that is chemically coupled with 1,4-benzenedicarboxylic acid residual ligand. The hybrid catalyst is characterized to exhibit an optimized surface electronic structure, which improves the intrinsic activity and selectivity. Operando characterization and theoretical simulations further reveal that the residual ligand functionalization significantly boosts the formation and facilitates the adequate binding of *OOH intermediates. Thus, the ligand-functionalized Ni(OH) 2 exhibits high HO 2 − selectivity (>90%) in 0.1 M KOH across a broad current density up to 200 mA cm −2 . Moreover, high HO 2 − production rate of 13.7 mol g cat −1 h −1 with significant accumulation of 2.0 wt.% HO 2 − under alkaline conditions is achieved at 200 mA cm −2 over 100 h, suggesting the promising potential for large-scale electrosynthesis of HO 2 − in industrial applications.
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CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Dongyao Yue,Zhe Wang,Jing Chang,Shaopo Wang,Jingjie Yu,Hongying Meng,Rui Zhang
In the O 3 self-decomposition process, the poor HO 2 − formation efficiency limits O 3 decomposition and •OH production. Although the addition of Fenton’s reagent facilitates this process, H 2 O 2 consumption and Fe(III) sedimentation must be addressed. In this study, carbon-coated Fe 3 O 4 (Fe 3 O 4 @C) samples were prepared using the metal–organic frameworks (MOFs) modification method for the catalytic ozonation of aromatics, which effectively solved the above challenges. The fabricated 4-Fe 3 O 4 @C catalyst not only exhibited a yolk-shell structure, but also increased •OH production by 9-fold, resulting in optimal target removal, mineralization, and O 3 decomposition efficiency. Further investigation confirmed that the activity of 4-Fe 3 O 4 @C was owing to the combined action of Fe(II) on the catalyst surface and the H 2 O 2 produced from aromatic degradation. Furthermore, the outer carbon layer with reducing properties regenerated Fe(II) in a timely manner, ensuring catalyst durability. Finally, a clear pathway for enhancing O 3 decomposition and •OH generation is proposed.
研究领域:
环境科学
·
材料科学
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ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2024
·
IF 10.8
Ying Chen,Lei Tian,Wen Liu,Yi Mei,Qiu-Ju Xing,Yi Mu,Ling-Ling Zheng,Qian Fu,Jian-Ping Zou,Daishe Wu
Dechlorination of chloropyridines can eliminate their detrimental environmental effects. However, traditional dechlorination technology cannot efficiently break the C–Cl bond of chloropyridines, which is restricted by the uncontrollable nonselective species. Hence, we propose the carbonate species-activated hydrogen peroxide (carbonate species/H2O2) process wherein the selective oxidant (peroxymonocarbonate ion, HCO4–) and selective reductant (hydroperoxide anion, HO2–) controllably coexist by manipulation of reaction pH. Taking 2-chloropyridine (Cl–Py) as an example, HCO4– first induces Cl–Py into pyridine N-oxidation intermediates, which then suffer from the nucleophilic dechlorination by HO2–. The obtained dechlorination efficiencies in the carbonate species/H2O2 process (32.5–84.5%) based on the cooperation of HCO4– and HO2– are significantly higher than those in the HO2–-mediated sodium hydroxide/hydrogen peroxide process (0–43.8%). Theoretical calculations confirm that pyridine N-oxidation of Cl–Py can effectively lower the energy barrier of the dechlorination process. Moreover, the carbonate species/H2O2 process exhibits superior anti-interference performance and low electric energy consumption. Furthermore, Cl–Py is completely detoxified via the carbonate species/H2O2 process. More importantly, the carbonate species/H2O2 process is applicable for efficient dehalogenation of halogenated pyridines and pyrazines. This work offers a simple and useful strategy to enhance the dehalogenation efficiency of halogenated organics and sheds new insights into the application of the carbonate species/H2O2 process in practical environmental remediation.
研究领域:
环境科学
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化学工程
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2018
·Vol. 26
·期 2
·1445-1454
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IF 2.8
Wang Daiyao,Zou Jing,Cai Huahua,Huang Yixin,Li Fei,Cheng Qingfeng
Advanced oxidation processes offer effective solutions in treating wastewater from various industries. The process of alkali-activated hydrogen peroxide (H 2 O 2 ) was superior for the treatment of alkaline dye wastewater because no additional reagents were required except H 2 O 2 . However, an important and interesting phenomenon had been observed that the primary reactive species were found different for degrading organic pollutants with the process of alkali-activated H 2 O 2 . Azo dye of Orange G (OG) and triphenylmethane dye of Rhodamine B (RhB) were chosen as the target organic pollutants. The influences of various parameters on OG and RhB degradation by alkali-activated H 2 O 2 were evaluated. Furthermore, different scavengers, including ascorbic acid, methanol, t -butanol, isopropyl alcohol, furfuryl alcohol, and nitro blue tetrazolium, have been tested to identify the active species involved in dye degradation, and it was found that O 2 ·− was mainly responsible for degrading OG, while HO 2 − anion was the primary oxidant for degrading RhB.
研究领域:
环境科学
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化学工程
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JOURNAL OF HAZARDOUS MATERIALS
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2021
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IF 10.588
Yang Jin,Zhicong Lu,Peng Zhang,Fan Li,Tong Li,Lili Zhang,Wenhong Fan,Chun Hu
Herein, a novel BiOBr photocatalyst with partial surface modification by graphitized C (BiOBr-C g ) was synthesized through a hydrothermal method with hydrothermal carbonation carbon (HTCC) as a slow-releasing carbon source and characterized by experimental and theoretical methods. BiOBr-C g exhibited excellent visible-light photocatalytic performance toward various refractory pollutants, such as bisphenol A, ibuprofen, ciprofloxacin, 2,4-dichlorophenoxyacetic acid, and diphenhydramine. The characterization results demonstrate that a strong molecular orbital interaction occurs between graphitized C and BiOBr, resulting in the formation of a new surface valence band on graphitized C. This not only promotes the oxidation of pollutants by surface holes but also reduces the recombination of carriers during the bulk phase transfer process, thereby increasing the number of photogenerated carriers. Intriguingly, the analytical results for degradation intermediates and other characterization techniques demonstrate that the pollutants adsorbed on the graphitized C of BiOBr-C g can be directly excited through light irradiation and react along the organic radical degradation pathway in addition to pollutant degradation by holes and HO 2 • /O 2 •- .
研究领域:
环境科学
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材料科学
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化学
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光催化
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污染控制
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