CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Chen Qiao,Zahid Usman,Tai Cao,Souleymen Rafai,Zhitao Wang,Youqi Zhu,Chuanbao Cao,Jiatao Zhang
High-valence Ni and Fe metal sites have demonstrated a crucial role in enhancing the catalytic performances of NiFe-LDH electrocatalysts in oxygen evolution reaction (OER). Although considerable OER catalytic performances achieved under high overpotential, the catalytic talent of NiFe-LDH electrocatalysts at low overpotential is rarely realized due to the absence of high-valence Ni and Fe sites. We herein report a surface engineering route to fabricate sulfated NiFe-LDH nanosheets via ion exchange strategy in sulfate-rich media. XPS results reveal a modified surface electronic structure with high-valence Ni and Fe after ion exchange reaction. Computational PDOS results suggest that computed d-band centers (ε d ) of Fe and Ni for sulfated NiFe-LDH show a significant downward shift resulting an increased valence of metal cation with orbital volume shrinkage. The high-valence Fe can facilitate a optimized multi-electron process of Ni center from [Ni II -OH] − /[Ni III -OH] − to Ni IV -OOH rather than Ni II /Ni III to Ni IV at low overpotential. The high-valence Ni can serve as the highly active center for O-O coupling during OER process. Combined with the synergetic action of high-valence Fe and Ni, the sulfated NiFe-LDH nanosheets exhibit much larger reaction kinetics and outstanding electrocatalytic activity on glassy carbon electrode (η 10 = 219 mV, η 50 = 288 mV) with a remarkable long-term stability.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2020
·
IF 16.683
Lihan Pan,Wen Shi,Tapas Sen,Lingzhi Wang,Jinlong Zhang
The role of high-valent Fe has rarely been explored in persulfate-based heterogeneous reaction. Herein, the existence of Fe(IV) is verified in a visible light-assisted FeTiO 3 /persulfate system using methyl phenyl sulfoxide as the probe. The FeTiO 3 /persulfate/light system is capable of selectively degrading aromatic compounds with lower ionization potentials including tetracycline and bisphenol A by photo-generated high-valent Fe(IV). The contributions from SO 4 ·- , · OH and 1 O 2 are excluded. The comparable efficiency in the dark requires higher dosages and suffers from a rapid deactivation. Based on XPS, Raman and EPR analyses, the poor dark activity is caused by the formation of a complex between in situ formed Fe(III) and SO 4 2- on the FeTiO 3 surface; this complex is, however, the key intermediate for Fe(IV) production under the light irradiation. This study reveals the long-ignored role of SO 4 2- as an abundant species in iron-based persulfate systems. We also call for re-evaluating the real oxidation mechanism in other persulfate-based reactions considering the different oxidation mechanisms of radicals and high-valent iron.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2023
·
IF 16.5
Ning Zhang,Jiayi Du,Na Zhou,Depeng Wang,Di Bao,Haixia Zhong,Xinbo Zhang
Proton-exchange membrane water electrolysis, particularly driven by renewable electricity, is a sustainable strategy for green hydrogen production . However, developing highly active and stable electrocatalysts to accelerate the oxygen evolution reaction (OER) remains challenging. Herein, we introduce an effective strategy for constructing high-valence metal-doped IrO x with abundant oxygen vacancies, while simultaneously enhancing the catalytic activity and stability of the acidic OER. The synthesized Ta-doped IrO x (350-Ta@IrO x ) exhibits ultramicroscopic nanoparticle morphology and abundant surface oxygen vacancies, enabling a rapid OER process with a low overpotential of 223 mV at 10 mA cm -2 and 147.7 times higher mass activity (1207.4 A g Ir −1 ) than that of commercial IrO 2 at 1.55 V versus the reversible hydrogen electrode. More importantly, 350-Ta@IrO x affords excellent stability with insignificant potential degradation after 500 h of electrolysis at 10 mA cm 2 , originating from the low operating potential and suppressed dissolution and oxidation of oxygen vacancy active sites via Ta doping. Density functional theory calculations suggest that Ta doping and oxygen defect engineering are effective in facilitating the nucleophilic attack of water molecules, thereby accelerating the rate-determining step toward high catalytic OER activity on Ta-doped IrO x . We anticipate that this study will provide an effective method to obtain active and stable electrocatalysts via high-valence metal doping.
研究领域:
化学
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材料科学
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能源科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Guangqin Gong,Jieshu Zhou,Xiulan Guo,Ruiyan Xie,Xiangke Zeng,Min Zhang,Kangni Wen,Tianding Hu,Shaoyun Shan,Kaili Yao
The development of efficient electrocatalysts for oxygen evolution (OER) is very important for the practical application of water decomposition technology. Promoting the formation of high-oxidation-state transition metal species in a hydroxide catalyst may improve its catalytic activity in the oxygen evolution reaction, which remains difficult to achieve with current synthetic strategies. Herein, we reported the synthesis of Fe x Mn y-x nanosheets on nickel foam substrate subsequently by phosphating treatment (Fe x Mn y-x P/NF). The Mn-mediated and phosphating synergistic promoting the formation of high-oxidation-state Ni and/or Fe for improved oxygen evolution activity. In-situ Raman spectroscopy showed that the incorporation of Mn and P into the NiFe hydroxide caused a cathodic shift of the NiFe hydroxide (2 + ) to NiFeOOH (3 + δ) transition potential. Density functional theory calculations suggested that an elevated oxidation state for NiFe by Mn-mediated decreased the energy barriers of the rate-determining step (*OH → *O). As a result, an overpotential of 208 mV was achieved at a current density of 10 mA cm −2 in 1 M KOH. This work provides a new strategy and a deep insight into the construction of efficient NiFe-based water oxidation electrocatalysts.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Ruoyu Wei,Mansheng Liao,Lidan Sun,Qingfeng Zhang,Hong Zhang,Lei Zhang,Zhongxin Song
Developing highly efficient and low-cost bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting poses significant challenges. In this study, a novel bifunctional electrocatalyst, Irn-CoMoPOx, was achieved via incorporating low-loading Ir single atoms and clusters with the high-valence Mo6+ modified CoPOx nanosheets. The Irn-CoMoPOx catalyst demonstrates remarkable low overpotentials of 222 mV and 36 mV for the OER and HER, respectively, in delivering a current density of 10 mA cm–2. When employed as both the anode and cathode catalyst in overall water splitting, the Irn-CoMoPOx∥Irn-CoMoPOx configuration exhibits a superior cell voltage of 1.53 V, outperforming the benchmark Pt/C∥IrO2 electrolytic cell (1.60 V) for achieving the current density of 10 mA cm–2. Benefiting from the high-valence of Mo species, the metal–support interaction of Irn-CoMoPOx was greatly strengthened, resulting in an order of magnitude increase in the mass activity of Ir for the HER. The high valence of non-noble metals plays a crucial role in tuning the local electronic configurations and optimizing the adsorption energies of the intermediates, which synergistically improves the overall performance of Ir in water splitting. The study provides valuable insights for future research in the utilization of Ir-based bifunctional catalysts for overall water electrocatalysis applications.
研究领域:
材料科学
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电化学
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催化反应
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2022
·Vol. 169
·期 7
·073505
·
IF 4.386
Su Yao,Jinxiao Du,Jieting Xiang,Shoulian Wei,Yanqing Liu,Hongwu Wang
A high voltage sonoelectrochemical method was proposed for the preparation of highly oxidized carbon nanosheets (hoCNSs) with good hydrophilicity and excellent electrocatalytic property for various compounds. It was found that the high electrolytic voltage played an important role in the hoCNSs' fragmentary appearance and excellent electrocatalytic property. The ultrasonic power further obviously improved the electrolytic efficiency. The very low concentration of electrolyte leads to a very simple post-treatment process. So this facile, low-cost and environmentally friendly method had great utility value for the preparation of hoCNSs.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ChemElectroChem
·
2021
·Vol. 8
·期 24
·4774-4780
·
IF 4.59
Xinyue Zhang,Yanling Qiu,Qin Li,Xuqiang Ji,Jingquan Liu
Graphical On the edge : High-energy interfaces with high-oxidation-state cations synergy were designed to induce lattice distortion. As-obtained Fe-o-NiAlOH presents super-hydrophilicity and excellent catalytical activity toward oxygen and hydrogen evolution reaction with 202 mV and 180 mV to drive 10 mA cm −2 , respectively. This work offers an effective well-defined electrocatalyst and shows the synergetic protocol of unstable high-oxidation-state cations and lattice defects for high-performance water decomposition catalysis. Interfacial structure engineering with multiple high-oxidation-state cations, especially those that show unstable higher-valence during catalysis towards superior electron synergy, for high-performance electrocatalysis is of great interest and full of challenges. Lattice distortion from lattice strain at phase boundaries as a result of interfacial structure engineering is also appealing. Fe oxyhydroxide containing Fe 3+ lead to unstable Fe 4+ with a short lifetime on edge/defect sites during steady-state water-oxidation catalysis. Such material was deliberately installed to achieve atom-scale combination with Ni 3+ relevant layered double hydroxide to construct high-energy interfaces for high-oxidation-state cations synergy and induce lattice distortion. The Fe-o-NiAlOH exhibited prominent property toward oxygen evolution reaction with 202 mV to drive 10 mA cm −2 . Fe-o-NiAlOH also showed hydrogen evolution reaction activity, requiring an overpotential of 180 mV for 10 mA cm −2 . Alkaline water electrolyzer with Fe-o-NiAlOH as both anodic and cathodic electrodes required only 1.64 V to reach 10 mA cm −2 . This work offers an effective well-defined electrocatalyst and shows the synergetic protocol of unstable high-oxidation-state cations and lattice defects for high-performance water decomposition catalysis.
研究领域:
材料科学
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催化化学
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能源转换
✓ 已验证
产品关联
DOI
高影响因子
Advanced Fiber Materials
·
2022
·Vol. 4
·期 4
·774-785
·
IF 12.958
Wu Zihe,Yang Jiehui,Shao Wenjie,Cheng Menghao,Luo Xianglin,Zhou Mi,Li Shuang,Ma Tian,Cheng Chong,Zhao Changsheng
Developing efficient and durable non-noble metal-based oxygen evolution catalysts is of great importance for electrochemical water splitting. Here, we report a new and facile strategy for controllable synthesis of high-valence Mo modified FeNiV oxides as efficient OER catalysts. The Mo-dopant displays a significant influence on the valence state of Fe species in the catalysts, which lead to tunable OER performance. When the feed ratio of Mo-dopant is 5%, the Mo-modified FeNiV oxide shows the best OER performance in terms of low overpotential (237 mV at the current density of 10 mA cm −2 ), Tafel slope (38 mV per decade), and high mass activity, which exceeds its counterparts and most reported OER catalysts. Furthermore, by assembling the catalyst with a carbon fiber cloth, the fabricated water-splitting device exhibits excellent activity and long-term durability in alkaline electrolyte compared with commercial catalysts equipped device. This work not only provides a series of Mo-modified FeNiV-based oxides as high-performance OER catalysts but also offers a new pathway to tune the charge states of OER active centers. Graphical abstract
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL IMMUNOPHARMACOLOGY
·
2023
·
IF 5.6
Pingchuan Wang,Tianming Li,Changping Niu,Siyu Sun,Dongyan Liu
Reactive oxygen species (ROS) damage to the intestinal barrier is a side effect of prolonged hyperoxia therapy in neonates, which impairs growth and development of the intestine and promotes intestinal diseases. However, the research on clinical prevention and treatment is lacking. Therefore, we investigated the molecular mechanisms of the neonate intestinal response against hyperoxia-derived ROS to find targets for intestinal barrier damage prevention. Human intestinal epithelial cells were incubated under hyperoxia (85% oxygen) to build an in vitro model. ROS and the mitogen-activated protein kinase (MAPK)/extracellular signal-regulated kinase (ERK) pathway were inhibited to detect the MAPK/ERK pathway, nuclear factor erythroid factor 2-related factor 2 (Nrf2), hypoxia-inducible factor-1α (Hif-1α), and interleukin-17D (IL-17D) expression. Nrf2 was inhibited to detect Hif-1α and IL-17D expression. Hif-1α was inhibited to detect Nrf2, IL-17D, and tight junction proteins expression and apoptosis. Cells were treated with human recombinant IL-17D to detect TNF-α, IL-1β, IL-10, and tight junction proteins expression. ROS, Nrf2, Hif-1α, and IL-17D were upregulated and the MAPK/ERK pathway was activated under hyperoxia. But ROS inhibition downregulated the MAPK/ERK pathway, Nrf2, Hif-1α, and IL-17D. MAPK/ERK pathway inhibition downregulated Nrf2, Hif-1α, and IL-17D. Nrf2 inhibition downregulated Hif-1α and IL-17D. Hif-1α inhibition downregulated Nrf2, IL-17D, tight junction proteins, and exacerbated apoptosis. The recombinant IL-17D downregulated TNF-α, IL-1β, but upregulated IL-10 and tight junction proteins. We concluded that Hyperoxia-generated ROS activated the MAPK/ERK pathway to regulate Nrf2, Hif-1α, and IL-17D expression. Nrf2 and Hif-1α were interdependent and promoted IL-17D. Importantly, Hif-1α and IL-17D expression protected the intestinal epithelial barrier.
研究领域:
分子生物学
·
细胞生物学
·
儿科
·
肠道生理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
BIORESOURCE TECHNOLOGY
·
2023
·
IF 11.4
Shuo Li,Yingnan Liu,Heshan Zheng,Junfeng Niu,Yoong Kit Leong,Duu-Jong Lee,Jo-Shu Chang
Corn straw and sludge-derived biochar composite (BC) loaded with CoFe 2 O 4 was successfully prepared to activate peracetic acid (PAA) for efficient degradation of tetracycline hydrochloride (TCH). Within 60 s, 96 % TCH removal efficiency was achieved through a non-free radical degradation pathway, primarily driven by singlet oxygen ( 1 O 2 ). The mechanism involves the electron-rich groups on the biochar surface, which facilitate the cleavage of the PAA O O bond to generate •O 2 − / 1 O 2 and provide electrons to induce the formation of high-valent Fe(IV) and Co(IV). The oxygen vacancies on the surface of the CoFe 2 O 4 -loaded biochar composite (CFB-2) contribute partially to 1 O 2 production through their transformation into a metastable intermediate with dissolved oxygen. Moreover, elevated temperatures further enhance PAA activation by CFB-2, leading to increased reactive oxygen species (ROS) production through PAA decomposition, thereby promoting TCH removal. This study offers new insights into the catalysis of metal-loaded biochar for efficient TCH degradation via non-free radical generation.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ang Li,Bin Li,Li-Ming Sun,Le-Xuan Liu,Chang Liu,Ya-Meng Dong,Xing Zhang
Advanced oxidation processes involving high-valent metal-oxo species have garnered increasing attention for their effective pollutant degradation in water. However, less is known about the mechanism of the species in the manganese oxides (MnO x ) system. Therefore, it is crucial to design MnO x catalysts to systematically clarify the high-valent metal-oxo species reaction mechanism. In this study, MnO x nanoplates including Mn 3 O 4 , Mn 5 O 8 , and Mn 2 O 3 were synthesized via a facile thermal treatment of a Mn(OH) 2 precursor to activate peroxymonosulfate (PMS) for mechanism studies. The Mn 3 O 4 catalyst exhibited superior catalytic performance and reusability owing to its unique spinel structure and rapid electron transfer properties. The first-order rate constant for Mn 3 O 4 is 0.64 min −1 , which is 3.7 and 1.5 times higher than those of Mn 5 O 8 and Mn 2 O 3 , respectively. Scavenging experiments, electron paramagnetic resonance, and electrochemical analysis revealed that free radicals played a negligible role, while the formation of high-valent Mn-oxo species was promoted, facilitated by the Mn 3 O 4 -PMS* complex. These high-valent Mn-oxo species were highly reactive towards various pollutants. Moreover, the degradation intermediates of bisphenol A (BPA) in the Mn 3 O 4 /PMS system were identified, further elucidating the interactions between high-valent Mn-oxo species and BPA. Additionally, the Mn 3 O 4 catalyst exhibited excellent catalytic performance under practical conditions and maintained superior stability over six cycles. This work provides crucial insights into the role of transition metal oxides in activating PMS for the catalytic degradation of emerging pollutants.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Acta Biomaterialia
·
2024
·
IF 9.4
Yanling Lin,Liyue Liu,Jiaqi He,Jianliang Shen,Qizhi Ren
The emergence of multidrug-resistant (MDR) bacteria represented by MRSA (Methicillin-resistant Staphylococcus aureus ) poses a great challenge to current anti-infection treatment. It is critical to develop efficient MRSA anti-bacteria drugs and explore simple therapeutic strategies with low MDR risk. Herein, we synthesized high-valent (Ag II /Ag III ) water-soluble porphyrins (cationic AgTMPyP and anionic AgTMPPS) and investigated their direct bactericidal property for MRSA without photoactivation in vitro and in vivo. The cationic porphyrin AgTMPyP exhibits well oxidase-like activity and has 100 % sterilizing rate at 8 μmol/L concentration. Besides, AgTMPyP can effectively destroy biofilms in vitro , mediate the polarization of macrophages from M1 to M2, and promote wound healing in vivo . Combined with DFT calculation, the related antibacterial mechanism is further discussed. High-valent silverporphyrins can maintain stable in water for at least 200 days. The moment they encounter MRSA, high-valent silver ions from AgTMPyP can be immediately released from the porphyrin ring and attack the MRSA with efficient sterilization. Together with the hemolysis, blood routine and blood biochemistry tests, it is proved that AgTMPyP can have great prospects in the direct treatment of bacterial infections in skin diseases in the future. Statement of significance The emergence of multidrug-resistant (MDR) bacteria represented by MRSA poses a great challenge to current anti-infection treatment. It has become critical to develop efficient MRSA anti-bacteria drugs and explore simple therapeutic strategies with low MDR risk. We synthesized high-valent (Ag II /Ag III ) water-soluble silver porphyrins (AgTMPyP and AgTMPPS), which can be stable for long periods in aqueous solutions. AgTMPyP can directly and efficiently kill bacteria and destroy biofilms without photoactivation in vitro and in vivo . Combined with DFT calculation, the related antibacterial mechanism is further discussed. AgTMPyP is a superior antimicrobial agent with good biocompatibility and it can have great prospects in the direct treatment of bacterial infections and wound healing in the future.
研究领域:
微生物学
·
药物化学
·
感染病学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）