APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Peng He,Chunyao Gu,Mengfei Liu,Jiancheng Chen,Junwen Chen,Junwu Liu,Yingchun Fang,Haijiao Xie,Jianyu Zhu,Min Gan
The treatment of emerging pollutants has become a challenging and multidisciplinary subject. Advanced oxidation processes based on persulfate are a strategic opportunity to address this issue, with research into catalysts and catalytic processes being the focus of this process. In this work, flower-like cobalt sulfide (F-CoS) particles acted as catalysts in peroxymonosulfate (PMS) activation for degrading an organic pollutant, sulfamethoxazole (SMX). The results indicated that F-CoS/PMS combined system performed excellently, with SMX being completely oxidized within 10 min. And the system exhibited superior resistance to environmental factors (e.g. pH and anions). Radicals quenching and electron paramagnetic resonance (EPR) analyses indicated that non-radical pathways based on high-valent cobalt-oxo (Co(IV)) species and 1 O 2 take a dominant position in SMX degradation, instead of SO 4 •− and •OH. Electrochemical, in-situ Raman and density functional theory (DFT) calculations revealed that PMS interacts with Co sites on the F-CoS surface, and then electronic transfer processes occurred, in which PMS acts as an electron acceptor to produce Co(IV) species and as an electron donor to produce 1 O 2 . This study not only implies a method with great potential application in organic wastewater treatment but also contributes to further comprehending the heterogeneous activation process and catalytic mechanism of PMS.
研究领域:
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Dingfeng Jin,Qiutong Zhao,Chen Wang,Yanxue Zhang,Junfeng Gao,Jungang Hou
Electrocatalytic oxidation of biomass-derived alcohols offers a sustainable pathway for the synthesis of high value-added chemicals from renewable carbon sources. However, multi-step electron transfer and intermediates-diversity in alcohol oxidation reactions (AOR) often result in low reactivity efficiency and poor product selectivity. Therefore, it is still highly desirable yet challenging to develop efficient catalysts for the electrosynthesis of carboxylic acids via AOR. Herein, taking AOR as the proof-of-concept reaction, earth-abundant NiCoO x nanosheets prepared by O 2 -plasma treatment demonstrate impressively high Faradaic efficiencies of 78.7–96.8 % for carboxylic acids electrosynthesis as well as low overpotentials (E 10 = 1.08–1.23 V vs. RHE at 10 mA cm −2 ). In situ spectroscopy and electrochemical measurements reveal that both Co 3+ and Co 4+ species formed on surface reconstructed (oxy)hydroxides are AOR active sites. Empirical evidence from isotope labeling and theoretical calculation demonstrate that lattice oxygen is activated and mediates in the oxygenation process of AOR, owing to the enhanced covalency of metal-oxygen bond and elevation of O 2p band center. This work has substantiated the direct participation of lattice oxygen in alcohol electrooxidation through compelling experimental and theoretical evidence, thereby offering valuable mechanistic insights into the biomass-derived chemical synthesis.
研究领域:
电催化
·
可再生能源化学
·
材料科学
·
物理化学
·
环境友好合成
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Yi Ren,Naiwen Li,Jun Li,Hailong Sun,Bo Lai
In this study, three different cobalt-doped graphitic carbon nitrides (Co/C3N4) were developed with precursors of urea, dicyandiamide, and melamine to activate peracetic acid. Optimal conditions of pH 4.0 and the cobalt ratio were obtained, with high decontamination performance and low leaching. Characterizations of Co/C3N4 indicate that Co/C3N4 synthesized with different precursors showed similar chemical and crystal structures while exhibiting differences in surface morphology and pore structure. Due to the high specific surface area and pore volume, Co/C3N4 with a precursor of urea showed the best activity, k1, for carbamazepine removal, which was 0.07193 min–1, higher than those with precursors of dicyandiamide (0.05084 min–1) and melamine (0.03499 min–1). The main active species for decontamination was identified by quenching experiments, chemical trapping, electron paramagnetic resonance analysis, and isotope labeling, and the results suggest that high-valent cobalt was the main active species and HO• showed minor efficiency for pollutant degradation. The degradation pathway of carbamazepine was proposed, and the results further confirm the main active species of high-valent cobalt, which mainly reacted with the amino group. Moreover, the practicability of Co/C3N4-activated peracetic acid was evaluated by recycling use, different pollutant treatments, and real wastewater treatment. The results indicate the systems showed better decontamination performance for carbamazepine, sulfamethoxazole, and bisphenol S, could effectively resist the interference of the substrate in real wastewater, and could efficiently remove CBZ within five reuse cycles. This study understood the activity and mechanisms of Co/C3N4-activated peracetic acid with different precursors, which might give new ideas on supporter structure design for Fenton-like catalysis improvement.
研究领域:
环境科学
·
催化
·
水处理
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Qi Zhang,Wei Li,Siyuan Cao,Xu Yin,Hongwei Zhu,Liankai Gu,Haoming Chen,Xiaoyuan Zhang,Weiqing Han,Kajia Wei
Precisely controlling atomic occupancy in edge-sharing sites remains challenging and limits the application of spinel oxides in advanced oxidation processes (AOPs). Herein, a series of inverse spinel oxides featuring edge-sharing Co Oh -O-Mn Oh (Oh means octahedral) configurations were designed to leverage inter-octahedral electronic redistribution and spin-state modulation, thereby enhancing catalytic performance for peroxymonosulfate (PMS) activation and pollutant degradation. The energy redistribution induced by this structure enhances the O-p/Mn-d orbital hybridization, accelerates the electron transfer kinetics between Co and Mn, and promotes the generation of high-valent cobalt-oxo (Co IV =O) species and singlet oxygen ( 1 O 2 ), thereby increasing the degradation efficiency of organic pollutants. The optimized Co-Mn inverse spinel achieved complete BPA removal within 15 min, exhibiting 11.4-fold enhancement in PMS activation efficiency than unmodified cobalt oxide, and with < 6.5 % average efficiency deviation at 100 mM ionic concentration. This study offers a strategy for the precise design of edge-sharing reactive sites in inverse spinel oxides and their application in AOPs.
研究领域:
环境催化
·
高级氧化技术
·
材料化学
·
无机化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Shizong Wang,Jianlong Wang
This study prepared the carbon-supported cobalt catalyst (Co-C-X) for activating peroxymonosulfate (PMS), and investigated the effect of co-pyrolysis temperature of graphitic carbon nitride (g-C 3 N 4 ) and vitamin B 12 on the catalytic activity. It was found that with the increase of co-pyrolysis temperature, the catalytic activity of Co-C-X increased, due to the different coordination structures of cobalt. At 500 °C (Co-C-500), cobalt existed as CoO; while it was single atom Co at 600 °C (Co-C-600); and small size CoO at 700 °C (Co-C-700). Co-C-X could activate PMS to produce hydroxyl radicals, sulfate radicals, high-valent cobalt-oxo and singlet oxygen, which depended on the pyrolysis temperature. Although Co-C-700 had the highest catalytic activity, the leaching cobalt was also highest (3.23 mg/L), compared with that of Co-C-500 (0.27 mg/L) and Co-C-600 (0.14 mg/L). Co-C-600 had fast degradation for atrazine, nitrobenzene , bisphenol A, phenol and 4-chlorophenol, which also had wide pH range and high tolerance to inorganic ions.
研究领域:
催化
·
环境科学
·
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）