INTERNATIONAL JOURNAL OF ENERGY RESEARCH
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2022
·Vol. 46
·期 15
·22782-22794
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IF 4.672
Zhijun Liu,Yegui Fang,Jianxin Wang,Chensheng Ma,Youkun Tao,Jing Shao
Summary The development of a cobalt-free cathode with long-term stability and high electrochemical activity is important for constructing low-cost and robust solid oxide fuel cells (SOFCs). Here, we report performance enhancement of a cobalt-free cathode achieved by valence regulation of the ferrite-based perovskite. Utilizing co-doping of high valence niobium with low valence nickel, we developed a cathode material La 0.8 Sr 0.2 Fe 0.8 Ni 0.15 Nb 0.05 O 3−δ that allowed representing adequate conductivity of 214 S cm −1 at 700°C, decent thermal compatibility with thermal expansion coefficient being 12 × 10 −6 K −1 , superior electrochemical properties manifested by area-specific resistance of 0.06 Ω cm 2 and peak power density of 760 mW cm −2 at 800°C, and excellent discharge durability of over 480 h at a current density of 460 mA cm −2 under 750°C. This significantly enhanced performance originates from a proper regulation of the electronic structure rendered by synergistic effects induced by the co-doping of the high valence niobium with low valence nickel into the B sites of the ferrite perovskite. Such a regulation enables an optimized compromise among the oxygen vacancies, electronic mobility, oxygen adsorption and dissociation, and strontium segregation.
研究领域:
材料科学
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能源科学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
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2023
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IF 7.7
Pengkun Zhang,Yujie Lai,Xinghua Dai,Yunzhuo Xu,Xinru Wu,Baoqian Yang,Dong-Hau Kuo,Dongfang Lu,Qinhan Wu,Mengistu Tadesse Mosisa,Jinguo Lin,Xiaoyun Chen
Tetragonal wakefieldite (CeVO 4 )-like CeVOS catalysts with exceptional performance in catalytic reduction of Cr 6+ , MB, and RhB pollutants in the presence of NaBH 4 under dark was prepared via a green and facile method. Hydrazine reduces V 5+ ions to elevate the V 4+ contents, and sulfur-doped is employed to balance lattice deviations from electrical neutrality induced by high V 4+ concentrations, enhancing overall stability. Hydrazine modulation regulates the V 4+ /(V 4+ +V 5+ ) ratio, influencing sulfur doping, defect structure, and electron transfer efficiency. The CeVOS catalyst with an optimized V 4+ /(V 4+ +V 5+ ) ratio of 0.46 with abundant oxygen vacancies and exhibited exceptional catalytic performance. The 100 mL 50 ppm Cr 6+ , MB, and RhB solution were completely reduced in 10 min and durable stability, after six runs, it still achieved a 98.8% reduction of Cr 6+ within 10 min. Response surface methodology (RSM) elucidated variable interactions and their influence on catalytic reduction performance. The model’s robustness is underscored by a predicted R 2 of 0.9345. Optimal conditions for pollutant treatment in practical applications are 15 mg of catalyst, 25 mg of sacrificial agent, and a pH value of 6.8. Therefore, the green synthesis of efficient CeVOS catalysts bears excellent promise for industrial wastewater treatment .
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
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
·
IF 21.1
Zichen Wang,Suhao Chen,Runzhe Chen,Haoran Jiang,Yinghui Jiang,Qiliang Wei,Wei Wu,Jun Zhong,Niancai Cheng
The sluggish kinetics of the oxygen evolution reaction (OER) caused by the complex process significantly hinder the advancement of electrolytic water to hydrogen technology. Herein, the valence of Ru is modulated and stabilized through inducing the electronic competition between Mo and Ru, and the charge transfer from Fe, Co, and Ni to Ru in 2D porous FeCoNiMoRu high entropy oxides (HEO) nanosheets to achieve efficient and stable OER. The 2D porous structure of FeCoNiMoRu HEO contributes to the high exposure of active sites while promoting rapid mass transfer, which can facilitate oxygen-evolving kinetics of the catalyst. Consequently, the optimized catalyst (FeCoNiMoRu HEO) surpasses RuO 2 (315 mV) in OER catalytic activity, exhibiting an overpotential of 226 mV at 10 mA cm −2 . Notably, the mass activity of FeCoNiMoRu HEO is nearly 18.6-fold that of RuO 2 . Combined experimental and theoretical analysis, a charge competition between Mo and Ru atoms, and the charge transfer from Fe, Co, and Ni elements to Ru in HEO can buffer the change of valence of Ru and modulate its electronic structure, thus enhancing the activity and durability of FeCoNiMoRu HEO during OER.
研究领域:
材料科学
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电化学
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纳米催化
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能源化学
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物理化学
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产品关联
DOI
高影响因子
Acta Biomaterialia
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2025
·
IF 9.6
Jing Yu,Chen Wang,Fan Zhao,Zhengtao Xu,Yuxin Zhang,Yao Ying,Wangchang Li,Juan Li,Jingwu Zheng,Liang Qiao,Shenglei Che
Inducing oxidative stress through metal ions activated biocatalysis is a fundamental mechanism of metal ion-interference therapy (MIIT). However, the actual catalytic efficiency of MIIT is often limited by the random valence states of metal ions and scattered space. Herein, copper-iron bimetallic sulfide nanoparticles coated with bovine serum albumin (CFS NPs) are synthesized through metal ion valence modulation strategy. Significant amounts of Cu⁺ and Fe²⁺ were released by CFS NPs, which is crucial for catalyzing Fenton-like reaction. The presence of Fe³⁺ further boosts Fe²⁺ availability and protects against hydroxyl radical (•OH) elimination via glutathione (GSH) consumption, amplifying the mitochondrial oxidative stress to induce apoptotic cell death. This oxidative stress damage is manifested in Cu + targeting the mitochondrial tricarboxylic acid (TCA) cycle, further causing proteotoxic stress and cuproptosis. The production of lipid peroxidation (LPO) and the inactivation of glutathione peroxidase 4 (GPX4) expression are also affected by the amplified oxidative stress to achieve efficient ferroptosis. As a result, the synergistic apoptosis/cuproptosis/ferroptosis multimodal therapy almost completely inhibits tumor growth in vivo. It is believing that CFS NPs provide feasible implications for multiple combination therapy of tumors with the rational regulation of metal ion valence state and precise spatial control to effectively improve the level of oxidative stress. Statement of Significance : Metal ion-interference therapy induces oxidative stress in tumor cells via metal ion-activated biocatalysis, influencing reactive oxygen species (ROS) levels, proteotoxic stress, and lipid peroxidation accumulation. However, the actual catalytic efficiency of metal ion-interference therapy is often limited by the random valence state of these metal ions and scattered space. Herein, we constructed variable valence copper-iron bimetallic sulfides nanoparticles (CFS NPs) through metal ion valence modulation strategy to overcome the key factors that constrain efficiency with the combination of triple oxidative stress spatially treatment for apoptosis/cuproptosis/ferroptosis therapy. The reduced acidity and GSH concentration within normal cells lead to a much low cytotoxicity to normal cells, and therefore higher biocompatibility and biosafety for bio-medical applications.
研究领域:
肿瘤学
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生物医学工程
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药理学
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产品关联
DOI
PubMed
高影响因子
Journal of Cleaner Production
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2022
·
IF 11.072
Linxuan Xie,Tianshu Zhang,Xinyu Wang,Wenxin Zhu,Zhaoli Liu,Manshun Liu,Jing Wang,Liang Zhang,Ting Du,Chengyuan Yang,Mingqiang Zhu,Jianlong Wang
Semiconductor-based photocatalyst , whose efficiency distinctly hinges on the separation of photoinduced charge transfer within the interface of bulk structure, has incurred some intractable issues due to the existing energy barrier. Regulating the structure of MOF reasonably would feature an accelerated charge separation, and an effective utilization of photogenerated charges. Herein, a new type of MOF with both interior linker and metal valence modulation (m-MIL-101–1.0) is reported to boost photocatalytic activity owing to the formed charge migration pathway. At first, we introduced defective sites via CTAB, which acted as exposed sites for further reduction reaction. Then, NaBH 4 was used to achieve metal valence regulation. Benefiting from the unique structure, the Fe 3+ /Fe 2+ redox center was considered as a driving force to facilitate the charge transfer. It is properly considered that the activity improvement is attributed to the synergistic effect of both internal and external charge transfer channels. As a result, such m-MIL-101–1.0 has a higher activity than that of MIL-101 for photocatalytic degradation of tetracycline in water. We envision this interior configuration would be an ideal paradigm for tuning the activity of MOFs and extending the boundaries of MOF-based photocatalysts.
研究领域:
材料科学
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环境科学
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化学
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产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
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2025
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IF 6.4
Jiayu Zheng,Longxiao Zhou,Qiufen Liu,Senwei Wu,Yuting Peng,Xiujian Zhao,Shouqin Tian
Ratiometric optical thermometry has emerged as a vital platform for non-contact temperature monitoring in industrial and scientific applications, demanding sensors with high sensitivity, non-invasiveness, and spatial resolution. Although zeolitic imidazolate framework-8 (ZIF-8) possesses attractive thermal stability and structural tunability, its limited luminescence intensity hinders practical thermometric applications. Meanwhile, ZIF-L, a two-dimensional (2D) polymorph of ZIF-8 with identical ligands, remains unexplored for temperature sensing. Herein, we propose a dual-modulation strategy synergizing lanthanide valence engineering with MOF phase control to develop a multi-emission center Eu3+/Eu2+ co-doped ZIF-L film (Eu/ZIF-L). By introducing Eu3+ into ZIF-8 precursors, the partial reduction of Eu3+ to Eu2+ under thermal treatment triggers a structural evolution from 3D ZIF-8 to 2D ZIF-L. The resultant Eu/ZIF-L exhibits dual emission peaks at 450 nm (Eu2+) and 495 nm (ligand-centered), with their intensity ratio (I495/I450) demonstrating remarkable linear temperature dependence over 296–373 K and achieving a relative sensitivity of 1.95% K−1. This work pioneers the integration of valence-state manipulation and MOF phase transition for thermometric optimization, providing a novel paradigm to design advanced ratiometric MOF thermometers for industrial thermal management.
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DOI
高影响因子
JOURNAL OF POWER SOURCES
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2025
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IF 7.9
Yaoxia Yang,Yu Zhang,Biaobiao Lu,RuiRui Zhang,Fuxing Zhou,Dongfei Sun,Xiaozhong Zhou,Zhiwang Yang,Ziqiang Lei
Designing and preparing bifunctional fully hydrated electrocatalysts through interface engineering and valence state modulation is an effective method to reduce the catalytic energy barriers for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). However, developing and constructing efficient, low-cost non-precious metal mixed catalysts pose significant challenges, especially in terms of metal electronic configuration and structural control. In this study, we prepared a nanoflower heterostructure array of copper iron sulfide and cobalt iron layered double hydroxide by copper doping and in-situ sulfurization of dynamically protected iron substrates. The construction of this heterostructure exposes more catalytic active sites and optimizes the electron arrangement of the catalyst, significantly enhancing the superhydrophilicity/superaerophobicity of the electrocatalyst and improving its catalytic activity and stability during the OER and HER processes. Density functional theory (DFT) calculations indicate that the synergistic regulation of cobalt and copper, along with the optimization of the sulfide, reduces the free energy required for OER intermediate adsorption, adjusts the surface electronic structure of the material, promotes electron transfer between the heterostructures, and accelerates the kinetics of the catalytic reaction. As a result, the prepared catalytic material exhibits excellent electrocatalytic performance for both OER and HER, requiring overpotentials of 285 mV and 72 mV, respectively, to achieve a current density of 10 mA cm −2 in an alkaline electrolyte (1 M KOH solution). The assembled electrocatalytic water splitting cell operates at a low voltage of only 1.53 V. This study provides an attractive approach for the future design of efficient water splitting electrocatalysts.
研究领域:
材料科学
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电化学
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纳米技术
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催化
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能量转换
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产品关联
DOI
高影响因子
Nano Research
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2024
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IF 9.5
Li Xinyang,Ding Binbin,Li Jing,Han Di,Chen Hao,Tan Jia,Meng Qi,Zheng Pan,Ma Ping’an,Lin Jun
Chemodynamic therapy (CDT), an inventive approach to cancer treatment, exploits innate chemical processes to trigger cell death through the generation of reactive oxygen species (ROS). While offering advantages over conventional treatments, the optimization of CDT efficacy presents challenges stemming from suboptimal catalytic efficiency and the counteractive ROS scavenging effect of intracellular glutathione (GSH). In this study, we aim to address this dual challenge by delving into the role of copper valence states in CDT. Leveraging the unique attributes of copper-based nanoparticles, especially zero-valent copper nanoparticles (CuPd NPs), we aim to enhance the therapeutic potential of CDT. Our experiments reveal that zero-valent CuPd NPs outperform divalent copper nanoparticles (Ox-CuPd NPs) by displaying superior catalytic performance and sustaining ROS generation through a dual approach integrating peroxidase-like (POD-like) activity and Cu + release. Notably, zero-valent NPs exhibit enhanced GSH depletion compared to their divalent counterparts, thereby intensifying CDT and inducing ferroptosis, ultimately resulting in high-efficiency tumor growth inhibition. These findings reveal the impact of valences on CDT, providing novel insights for the optimization and design of CDT agents.
研究领域:
纳米技术
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癌症治疗
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材料科学
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生物化学
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产品关联
DOI
高影响因子
FOOD CHEMISTRY
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2025
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IF 9.8
Mai Luo,Yao Peng,Jihai Cai,Tiantian Jiang,Sheng Gong,Shiyao Hua,Ting Wang,Sijia Wu,Shuangpeng Wang,Jinchao Wei,Peng Li
Pesticides play a crucial role in crop production. However, they also pose significant pollution and health risks. This study presents a novel dual-mode cascade strategy for detecting pesticide residues, addressing the growing demand for improved safety control. The proposed method utilizes a bifunctional metal-organic framework nanozyme (BMFN) with both fluorescence and biomimetic capabilities, enabling efficient analysis of pesticide residues. The bifunctionalities of BMFN is achieved by modulating Ce 3+ /Ce 4+ valence states and adjusting reaction conditions. The dual functionality is activated by changing the solvent pH, and its mechanism is thoroughly validated. Exposure to methyl paraoxon (MP) triggers a cascade reaction that generates both fluorescence and colorimetric signals, with detection limits of 0.2 and 0.5 μM, respectively. The effectiveness of the dual-mode strategy is demonstrated in complex matrices. Overall, the integrated system highlights the exceptional performance of the bifunctional nanozyme in chemical sensing and demonstrates the success of dual-mode cascade analytical approaches.
研究领域:
分析化学
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纳米技术
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环境科学
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生物传感器
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED MATERIALS
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2025
·Vol. 38
·期 3
·e10760
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IF 26.8
Jing Li,Xiaotao Zhang,Jinpeng Li,Xiaoyu Zheng,Minghui Li,Jiadong Zhou,Erhong Song,Yao Zhou
Metal-based site, as an important type of active site, plays the benchmarking role in the redox and charge transfer processes in the heterogeneous catalysis. Modulating the valence state of metal site as a promising and simple strategy theoretically enables control over the adsorption strength of reaction intermediates. However, this strategy is intrinsically limited by the local atomic configuration, often leading to unpredictable catalytic failures. Here, it is reported that the intermediate adsorption strength of platinum active site with different valence states exhibits a linear relationship with the d-band width of Pt (W d -Pt ). Adjusting the nearest-neighbor coordination environment of Pt sites by changing the transition metals bonded to Pt effectively modulates the W d -Pt , which offers a high activity (η 10 = 14 mV) in the hydrogen evolution reaction (HER). W d -Pt broadening elevates the Pt─H anti-bonding states across the Fermi level, strengthening active site-absorbate interactions and thereby tuning HER catalytic activity. In addition, this d-band width engineering strategy can be expanded to other catalysts with the metal active site. The present study transcends limitations in valence state modulation and sheds light on deeper understanding of d-band structure of metal sites and a methodology to boost the activity of metal sites in heterogeneous catalysis.
研究领域:
催化化学
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材料科学
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物理化学
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电化学
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纳米材料
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产品关联
DOI
PubMed
高影响因子
ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Yufeng Zhang,Jie Wang,Mingyue Tan,Ziyan Wang,Wanglai Cen,Luming Li,Longhua Zou,Hui Kang,Ming Li,Xu Wang,Ning Wang,Si Chen,Yachao Zhu,Jie Deng
The high-energy barrier and sluggish kinetics hinder the conversion efficiency of electrocatalytic water splitting. These limitations can be mitigated by modulating the valence states of active sites in nonprecious metal catalysts. However, achieving the synchronous but opposite valence regulation of different metals in multicomponent electrocatalysts remains a formidable challenge, especially when using one-pot synthesis methods. Here, we propose a phosphate anion modification strategy to endow the self-supporting NiCo materials (NiCoP@NF) with efficient water-splitting performance. The phosphate species, amply incorporated via one-step electrodeposition, form Ni–phosphate–Co-bridging motifs in which phosphate anions serve as efficient electron conducting pathways, rapidly shutting electrons from Ni to Co. Experimental analysis and theoretical calculations reveal that this electron shuttling effect induces the electron delocalization and redistribution around Ni and Co centers, simultaneously triggering the low valence state of Co and the high oxidation state of Ni in the integrated NiCoP@NF catalyst. The valence-modulated metal sites own the rapid hydrogen diffusion speed and deprotonation rate, obviously diminishing the energy cost for the phase transformation of Ni2+/3+ into high valent Ni3+σ/3+ as active oxygen evolution reaction (OER) phases, inducing the high-level nonconcerted proton electron transfer process during OER. Finally, NiCoP@NF exhibits excellent bifunctional electrocatalytic performance, with a low overpotential of 50.2 mV for hydrogen evolution reaction (HER) and an overpotential of 240 mV for OER at 10 mA cm–2. It also demonstrates great durability, maintaining an industrial current density of 1 A cm–2 for ultralong 10,127 h stability, showing competitive performance compared to most reported catalysts. Our study not only validates an effective valence regulation strategy in the mixed metal materials for achieving superb bifunctionality but also provides new insights into designing robust multinary transition metal electrocatalysts via oxyanion-induced electron bridging, offering promising prospects for industrial applications.
研究领域:
能量转换
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电化学
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催化
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材料科学
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纳米技术
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可持续能源
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氢能技术
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产品关联
DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
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2025
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IF 5.4
Linzhu Zhang,Quan Xiang,Ruoweng Liang,Guiyang Yan,Zhiyu Liang,Renkun Huang
Cerium-based metal-organic frameworks (Ce-MOFs) are emerging as hierarchical photocatalysts with tunable electronic structures, demonstrating significant potential for tetracycline (TC) degradation. In this work, mixed-valence cerium metal-organic framework (MVCM) was synthesized by a one-step partial oxidation strategy. Various characterization techniques were systematically employed to investigate the morphology, structure and optical properties of MVCM. It was found that multivalent regulation could enhance the visible light response and inhibit the recombination of photoinduced charges, thus overcoming the drawback of conventional Ce-MOF. When tetracycline was used as the target pollutant, the degradation rate of MVCM-1.0 reached 95 % after 80 min of illumination, which was ninefold higher than that of the pristine Ce-MOF. Moreover, the MVCM-1.0 exhibite excellent stability and recyclability. The degradation mechanism was analyzed through various approaches, including active species trapping experiments, electron paramagnetic resonance measurements, and relevant electrochemical analyses. In addition, the main degradation products and the possible decomposition routes of TC were inferred by combining liquid chromatography-mass spectrometry (LC-MS). This work deepens the understanding of the internal relationship between the structure and performance of photocatalysts.
研究领域:
材料科学
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环境科学
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无机化学
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光催化
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纳米技术
✓ 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）