INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Qian-Wen Lu,Qing He,Qing-Shuai Zhang,Da Sheng,Song-Hai Wu,Yong Liu,Xu Han
Although thermocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-formylfuran (DFF) by O2 is an important reaction, achieving a high yield of DFF is still challenging. In this study, a series of MoxCuy/NH2-SBA-15 are prepared, and Mo3Cu1/NH2-SBA-15 exhibits the desirable catalytic reactivity with a complete conversion of HMF and high selectivity of 94.4% toward DFF. XPS and EPR analyses indicate that the abundant oxygen vacancies (Ov) and Cu(I) are the reactive sites for O2 activation. Quenching experiments and various characterizations reveal that superoxo (≡Cu(II)/Ov-OO•) on the surface of catalyst, instead of •OH and O2•–, are the primary oxidizing species to abstract H from HMF to RCH2-O•, accompanied by the formation of ≡Cu(II)/Ov-OOH peroxo. Meanwhile, the doped Mo(V/VI) further activates ≡Cu(II)/Ov-OOH peroxo to form ≡Mo-(η2-O2) peroxo, which significantly promotes the oxidation selectivity of RCH2-O• toward DFF via the H-abstraction pathway. This study provides new insight on selective thermal-oxidation of biomass-derived compounds to high-value-added chemicals via regulating reactive oxidizing species on the surface of catalysts.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2024
·
IF 15.7
Meiyun Zhang,Penghua Che,Hong Ma,Xin Liu,Shujing Zhang,Yang Luo,Jie Xu
Clean catalytic oxidation has a broad prospect in the modern chemical engineering and energy chemistry fields. However, unexpected over-oxidation and disruptive degradation are frequently induced by excessive reactive oxygen species (ROS). Herein, we reported a new ROS-free approach to effectively drive O 2 to be activated into highly reactive surface peroxo species through enzyme-mimicking mechanism. Benefiting from the dual-metal synergy effect between Cu and Co active sites, ROS (H 2 O 2 and OH • ) is generated in situ while further scavenged completely into surface peroxo species, which gives rise to very high selectivity and extremely high carbon balance. For example, the CuCo/N-C catalyst affords >99.8% conversion and 94.5% selectivity to 2,5-furanedicarboxylic acid at 25 °C for 6 h in the aerobic oxidation of biomass platform 5-hydroxymethylfurfural. Moreover, it achieved exceptional performance in the oxidation of a variety of hydroxyl compounds to organic acids with high yields (89.9%–99.5%) at a mild temperature (25–40 °C). This exploration introduces an innovative clue for emulating enzyme catalysts, thereby enriching our comprehension and advancement of biologically inspired catalytic oxidations.
研究领域:
催化化学
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能源化学
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生物仿生学
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DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
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IF 4.7
Xiaomei Yu,Junwei Xu,Liang Guo,Jieqi Zhou,Rumeng Ouyang,Xiuzhong Fang,Jiating Shen,Xiang Wang
At present, there are still controversy viewpoints on the reactive oxygen sites in the OCM reaction on ABO3 perovskites. Some researchers believe that electron-deficient chemisorbed oxygen species (O2–, O22–, and O–) contribute to C2 product formation, and surface lattice oxygen (O2–) promotes the deep oxidation of methane, while others hold an opposite viewpoint. In addition, the influence of BOx polyhedra on the reactive sites and reaction performance has rarely been elucidated. Considering this, two types of LaAlO3 perovskites, comprising different contents of surface and bulk coordinatively unsaturated sites (AlO4 tetrahedra), were synthesized for the OCM reaction. Through a series of in situ and ex situ characterization techniques and combined with DFT calculations, a high oxygen vacancy concentration was revealed for the AlO4-rich LaAlO3 perovskite, leading to an abundance of reactive oxygen and promoting oxygen mobility. The study identified monatomic surface lattice oxygen O2– as the active sites for the deep oxidation of methane at low temperatures. The O22– species generated by oxygen vacancies promotes the formation of C2 products at high temperatures.
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DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2021
·
IF 4.126
Dai Sun,Yu-Le Wang,Peng-Yue Zhu,Hai-Tao Ren,Yong Liu,Song-Hai Wu,Shao-Yi Jia,Xu Han
Mechanisms involved in the photocatalytic oxidation of As(III) are complicated in that various oxidizing species (such as h+, •OH, and O2•–) have been suggested to play important roles in different photocatalytic systems. In this study, Bi2.15WO6 shows high reactivity in the photocatalytic oxidation of As(III) under visible light. Quenching experiments indicate that apart from h+, the surface superoxo (≡Bi–OO•) and peroxo species (≡Bi–OOH) formed on Bi2.15WO6 also contribute to As(III) oxidation. The increased production of H2O2 with increasingly consumed As(III) or with the addition of H-donors such as glucose and various phenolics further reveals that H-abstraction from As(III) or H-donors to ≡Bi–OO• and then to ≡Bi–OOH is an important pathway involved in H2O2 production and As(III) oxidation. In addition, various characterizations confirm that the As(III)–O–Bi(III) surface complexes formed on Bi2.15WO6 enhance the photocatalytic reactivity of Bi2.15WO6 via the ligand-to-metal charge transfer pathway. We therefore suggest that dissolved oxygen is sequentially reduced to ≡Bi–OO• and then to ≡Bi–OOH on Bi2.15WO6, accompanied by H-abstraction from adsorbed or aqueous As(III) to ≡Bi–OO• and ≡Bi–OOH with the formation of H2O2 and the oxidation of As(III). This work enriches our understanding of the mechanisms involved in the photocatalytic oxidation of As(III).
研究领域:
环境科学
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材料科学
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DOI
高影响因子
Materials
·
2025
·Vol. 18
·期 11
·2544
·
IF 3.2
Qingyang Zhou,Zhuluni Fang,Junyi Wang,Wenbo Zhang,Yihan Liu,Miao Yu,Zhuo Ma,Yunfeng Qiu,Shaoqin Liu
Food spoilage caused by microbial contamination remains a global challenge, driving demand for sustainable antibacterial packaging. Conventional photocatalytic materials suffer from limited spectral response, rapid charge recombination, and insufficient reactive oxygen species (ROS) generation under visible light. Here, a Z-scheme heterojunction was constructed by coupling zeolitic imidazolate framework-8 (ZIF-8) with Ag 3 PO 4 , achieving dual-spectral absorption and spatial charge separation. The directional electron transfer from Ag 3 PO 4 ’s conduction band to ZIF-8 effectively suppresses electron-hole recombination, prolonging carrier lifetimes and amplifying ROS production (·O 2 − /·OH). Synergy with Ag + release further enhances bactericidal efficacy. Incorporated into a cellulose acetate matrix (CAM), the ZIF-8/Ag 3 PO 4 /CAM film demonstrates 99.06% antibacterial efficiency against meat surface microbiota under simulated sunlight, alongside high transparency. This study proposes a Z-scheme heterojunction strategy to maximize ROS generation efficiency and demonstrates a scalable fabrication approach for active food packaging materials, effectively targeting microbial contamination control and shelf-life prolongation.
研究领域:
材料科学
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食品科学
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微生物学
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产品关联
DOI
PubMed
高影响因子
ACS Applied Energy Materials
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2022
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IF 6.959
Xiaoshuang Kang,Guohui Dong,Tingting Dong
In this study, TiO2 samples are synthesized through two stages including hydrolysis and calcination. It is found that the addition of HCl in the hydrolysis stage could facilitate the formation of heterophase junction TiO2. By annealing at 300 °C in an argon atmosphere, interfacial oxygen vacancies (Vo) and surface Vo (distributed in the anatase phase) can be constructed in the heterophase junction TiO2. After photocatalytic experiments, it can be found that surface Vo and interface Vo have a synergistic effect in the production of photocatalytic reactive oxygen species (ROSs). Surface Vo can enrich O2 and transmit electrons to O2 on the surface of anatase. Therefore, the enriched O2 can be converted into •O2– and 1O2 easily. The interfacial Vo not only facilitate the electron transmission between the two phases but also change the electron transfer mode from I-scheme to Z-scheme. Thus, interfacial Vo make photogenerated electrons transfer to anatase and photogenerated holes leave in the rutile. These holes in the rutile part have high oxidation potential and can better oxidize H2O (or OH–) molecules to •OH. They can also oxidize •O2– to 1O2. This work promotes the further development of defect design and application in photocatalytic materials.
研究领域:
材料科学
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环境科学
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产品关联
DOI
高影响因子
Catalysts
·
2023
·Vol. 13
·期 3
·490
·
IF 3.9
Wenrui Zhang,Meilu Hao,Yonghui Wang,Pengfei Sun,Dongjuan Zeng,Xinya Wang,Peng Liang
Layered δ-MnO2catalysts were prepared using the one-step redox method in precursor solutions with five different pH values (pH = 7, 9, 11, 13, and 14). The effects of pH on the physical properties and catalytic activity of the catalyst were investigated through XRD, SEM, TEM, BET, XPS, H2-TPR, and HCHO degradation tests at room temperature. The results showed that the layer spacing, manganese vacancy content, Mn4+/Mn3+ratio, and surface-reactive oxygen species content of MnO2increased with the increase in pH value in the alkaline range. When the catalyst was prepared at pH = 13, the above characteristics of the catalyst reached the optimal value which contributed to the high catalytic activity. Combined with the related characterization results, it was proved that changing the pH can affect the degree of oxidation in the catalyst synthesis process, increase the number of active oxygen and the oxygen mobility of the catalyst, and effectively improve the catalytic activity of the manganese dioxide catalyst for HCHO. This work represents a giant step toward the preparation of an effective catalyst for practical applications of HCHO removal at room temperature at a low concentration and high velocity.Keywords:δ-MnO2;pH;formaldehyde;manganese vacancy;surface-reactive oxygen species
研究领域:
催化
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环境科学
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材料科学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Ziwei Gao,Tao Zhang,Md. Nahid Pervez,Guojuan Qu,Wei Jin,Yaping Zhao
Materials combing catalytic and adsorption dual active sites are very important for arsenite (As(III)) due to its high mobility in water. Therefore, in this study, a bifunctional walnut-like Co-doped La(OH) 3 composites (Co-La) with independent catalytic sites and post-formed adsorption sites were synthesized via a simple hydrothermal method. Nearly 100% As(III) removal can be achieved in Co-La and peroxymonosulfate interaction systems (Co-La/PMS) within 10 min at the molar ratio of PMS to As(III) of 1.2. The results indicate that the combined Co-La adsorption system demonstrated superior performance compared to the Co-La adsorption alone. Precisely, the maximum removal capacity of the system was measured at 243.90 mg·g −1 , and the pseudo-first-order kinetic rate constant ( k 1 ) was determined to be 1.0771 min −1 . These values were significantly greater than those observed for Co-La adsorption alone. Notably, the kinetic rate constant was 239 times faster, and the removal capacity was 4.6 times higher in the combined system. The fast kinetics of As(III) elimination can be elucidated by the production of reactive oxygen species (ROS) such as S O 4 · - , •OH, O 2 · - and 1 O 2 , which expedite the conversion of As(III) into arsenate (As(V) in this particular system. Meanwhile, the increase in adsorption capacity is ascribed to the fact that PMS can drive La(OH) 3 of Co-La to transform into transition states La 2 SO 4 (OH) 4 , thus generating a new exchangeable adsorption site for As(V). A fixed membrane reactor assembled with Co-La was utilized to achieve a near-complete removal of As(III) within 3 min. The Co-La/PMS systems demonstrate exceptional effectiveness in eliminating arsenic from water across diverse real-water metrics, offering a unique perspective and technological progress in purifying water contaminated with arsenic.
研究领域:
环境科学
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材料科学
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产品关联
DOI
高影响因子
Journal of Inorganic and Organometallic Polymers and Materials
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2025
·
IF 4.9
Liu Li,Lai Dengwang,Cao Wuyan,Bao Zanjuan,Zhao Tian,Wang Chunhua,Liu Yuejun,Yang Jun
This study synthesized zeolitic imidazolate framework (ZIF-8) using a solvothermal method and employed mechanical stirring to coat basic magnesium hypochlorite (BMH) onto the surface of ZIF-8, thus preparing antibacterial microspheres of BMH/ZIF-8. Escherichia coli ( E. coli ) was used as the model bacterium, the effect of BMH concentration on the antibacterial effect of BMH/ZIF-8 was explored, and the optimal BMH concentration was determined to be 100 µg/mL. The antibacterial rate was 73% for BMH, 20% for ZIF-8, and 100% for BMH/ZIF-8, as determined by the plate counting method. In addition, the synergistic effect factor (SEF) determination method calculated SEF > 0. This shows that BMH and ZIF-8 had a synergistic antibacterial effect. Important techniques such as Scanning Electron Microscope (SEM), Brunauer-Emmett-Teller (BET), and X-ray Diffraction (XRD) analysis were employed to investigate the synergistic antibacterial mechanism of BMH and ZIF-8. The mechanism is that porous ZIF-8 with ultra-large specific surface area cooperates with BMH to antibacterial. This synergistic effect allows BMH sheets to be adsorbed on the surface of ZIF-8, greatly increasing the contact area between the antibacterial agent BMH and bacteria. Additionally, BMH adsorbed on the surface of ZIF-8 can also serve as surface protection, thus delaying the breakage of Zn-N coordination bonds within ZIF-8. Consequently, as BMH on the surface of ZIF-8 is gradually consumed, the Zn-N coordination bonds undergo breakage, leading to slow release of internal Zn 2+ and 2-methylimidazole organic ligands. Zn 2+ possesses oxidizing properties, enabling it to bind with bacteria and disrupt their protein structures. Meanwhile, 2-Methylimidazole can undergo degradation, resulting in the generation of reactive oxygen species (ROS). The hydrophobic methyl group of 2-Methylimidazole is also able to compromise the integrity of bacterial membranes and impede the activity of key enzymes by means of chelating metal ions. Collectively, these mechanisms, in conjunction with ROS, establish a multifaceted antimicrobial network, thereby engendering a favorable antimicrobial effect.
研究领域:
材料科学
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微生物学
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医学
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产品关联
DOI
高影响因子
CHEMOSPHERE
·
2018
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IF 4.427
Xinghao Wang,Jiayi Yao,Siyuan Wang,Xiaoxue Pan,Ruiyang Xiao,Qingguo Huang,Zunyao Wang,Ruijuan Qu
Photodegradation of pollutants is classically explained by reaction with reactive oxygen species. However Mn(III) may also remove pollutants, but direct evidence is actually lacking. Here we investigated the role of soluble Mn(III) on phototransformation of four typical estrogens, namely estrone (E1), 17β-estradiol (E2), estriol (E3), and 17α-ethynylestradiol (EE2), in the presence of Mn(II) and humic acid . Conversion rates of 60.2%, 89.0%, 87.6%, and 80.2% were achieved for E1, E2, E3, and EE2, respectively, after 72 h visible light irradiation. A detailed quenching experiments revealed that soluble Mn(III), and not reactive oxygen species, was the oxidant responsible for estrogen removal. The determination of Mn(III) concentration provided direct proof of the role of Mn(III)-based oxidizers in the conversion of estrogens. Soluble Mn(III) can form complexes with humic acid, and about 6.51 μM of Mn(III)-humic acid was formed from 20 μM of Mn(II) in the presence of 5 mg/L of humic acid. Furthermore, product identification and theoretical computation demonstrated that estrogens are mainly converted into oligomers (dimers, trimers, tetramers, etc.) via a single-electron process. According to these results, the oxidation of Mn(II) to Mn(III) is initiated by superoxide ion (O 2 •- ) generated from dissolved oxygen in the presence of humic acid under visible light irradiation. The formed soluble Mn(III) strips the estrogens of a single electron to generate phenoxyl radicals, which undergo oligomerization, while leads to regeneration of Mn(II). Hence, the photochemical Mn(II)-Mn(III) redox cycling may significantly influence the fate and transformation of estrogens in waters.
研究领域:
环境科学
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生物学
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DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2022
·Vol. 29
·期 29
·43984-44002
·
IF 5.19
Liu Anchen,Lin Wenting,Ping Senwen,Guan Wenqi,Hu Ningyi,Zheng Sichun,Ren Yuan
Antihistamines (ANTs) are medicines to treat allergic diseases. They have been frequently detected in the natural water environment, posing potential threats to the ecological environment and human health. In this study, the degradation of three common antihistamines, loratadine, fexofenadine, and cetirizine, was estimated under different oxidation methods (NaClO, UV, and UV-NaClO). The results showed that UV-NaClO had the highest degree of degradation on the drugs under most conditions: 100% degradation for fexofenadine within 20 s at pH 7 and 10. Under UV irradiation, the degradation efficiencies of the three drugs during 150 s were all above 77% at a pH of 7. The drugs’ removal by NaClO was much lower than that of the previous two methods. In addition, this study explored the contribution rates of active oxygen species in the photolysis process. Among them, the contribution of 1 O 2 to the fexofenadine and cetirizine removal rate reached 70%. Different aqueous matrices (HCO 3 − , NO 3 − , and humic acid) had varying degrees of influence on the degradation. Acute toxicity tests and ultraviolet scans of the degradation products showed that the drugs were not completely mineralized, and the toxicities of the intermediates were even higher than those of the parent drugs. There were 9, 8, and 10 chloride oxidation products of loratadine, fexofenadine, and cetirizine, respectively, and 8 photolysis products of cetirizine were identified. For cetirizine, it was found that there were three identical intermediates produced by photodegradation and NaClO oxidation. Graphical abstract
研究领域:
环境科学
·
药理学
·
毒理学
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DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2025
·
IF 9
Yingying Fan,Junjie Liu,Xu Han
Photocatalytic generation of oxidative free radicals is an effective method to eliminate viruses and bacteria in air. Nevertheless, the underlying mechanisms governing the gas-phase sterilization remain unclear. In this study, the self-doped Bi 2.15 WO 6 was synthesized to prepare the Bi 2.15 WO 6 coating. In the presence of Bi 2.15 WO 6 coating, the average logarithmic degradation efficiencies ( LDEs ) are 3.82 and 3.07 for E. coli and S. aureus , respectively under UV illumination for 12.9 s, indicating its desirable sterilization efficiencies. In addition, the sterilization rates of E. coli and S. aureus slightly decrease by 3 % and 6 % after 30-repeated cycles, indicating the high stability of this catalytic coating. The 2,7-dichlorofluorescein (DCF) fluorescence experiments and SEM analysis indicate that reactive oxygen species (ROS) produced by Bi 2.15 WO 6 have effectively destroyed cell structure to achieve the complete inactivation. The N,N -diethyl-p-phenylenediamine sulfate (DPD) and radical trapping experiments further reveal that H 2 O 2 is the primary oxidizing species, and its yields are linearly proportional to the LDE values. The produced H 2 O 2 is further decomposed to •OH under UV irradiation to kill bacteria. Raman analysis confirms the presence of the intermediate species of surface ≡Bi-OO• superoxo and/or ≡Bi-OOH peroxo groups on Bi 2.15 WO 6 , which are the precursors of H 2 O 2 . In addition, the 3-D filter facilitates sterilization by the Bi 2.15 WO 6 in that it prolongs the duration of free radical via physically intercepting bioaerosols, thus apparently improving the degradation rate. This study provides new insights on the sterilization mechanism involved in the gas-phase photocatalytic processes.
研究领域:
环境科学
·
生物学
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产品关联
DOI
高影响因子
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