CHEMICAL ENGINEERING JOURNAL
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2026
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IF 12.5
Zening Pan,Yudie Fu,Jiayu Wu,Aihua Xu,Xiuying Liu,Shuaiqi Zhao,Xiaoxia Li
Vacancy electronic quality, not quantity, governs catalytic performance. • Co-doping and quenching construct asymmetric Co–Ov–Mo motifs, transforming inert deep traps into active shallow donors. • CMO-Q activates PMS through a dual non-radical pathway. The electronic structure characteristics of oxygen vacancies (O v ) - rather than their quantity - are the fundamental factors determining peroxymonosulfate (PMS) activation. This study proposes a strategy of cobalt doping and controllable quenching to precisely construct two types of O v configurations with distinct electronic properties in MoO 3 : the symmetrical Mo–O v –Mo coordination structure in MoO 3 -Q and the asymmetrical Co–O v –Mo coordination structure in CMO-Q. Comprehensive multimodal characterizations confirm that although MoO 3 -Q has the highest O v concentration (39.78%) and the strongest EPR signal, the significantly broadened tail feature in its valence band XPS spectrum clearly indicates that the vacancies exist in the form of deep-level trap states, making it difficult for the captured charges to participate in subsequent interfacial reactions, thus presenting electronic inertness. In contrast, cobalt doping plays a directional anchoring role in the lattice, guiding the vacancies to preferentially form in the Co-adjacent coordination environment. The constructed asymmetrical Co–O v –Mo structure induces an internal polarization electric field due to the difference in electronegativity between Co 2+ and Mo 6+ , forming a shallow donor state with electron-donating function, thereby endowing the vacancies with intrinsic electronic activity. The electrochemical tests quantitatively reveal the essential differences in interfacial charge transfer kinetics between the two: CMO-Q exhibits the largest open-circuit potential shift (0.59 V ) and the smallest peak potential difference (ΔE = 0.13 V ), while MoO 3 -Q shows the smallest shift (0.47 V ) and the largest ΔE (0.26 V ). Further normalization by the electrochemically active surface area (ECSA) highlights the intrinsic activity difference: the k obs /C dl of CMO-Q reaches 6.18 min −1 ·cm 2 ·mF −1 , which is ten times higher than that of MoO 3 -Q (0.62 min −1 ·cm 2 ·mF −1 ). This work establishes vacancy quality over quantity as the design principle for high-performance catalysts.
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高影响因子
ACS Applied Materials & Interfaces
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2025
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IF 8.2
Junfang Ding,Changjin Xu,Xinyi Yao,Kunming Hou,Yinkang Yang,Dan He,Hao Chai,Xiaomin Sun,Shanghong Zeng
The development of ultrafine metal oxide nanoparticles anchored on reducible oxide supports with precisely engineered interfacial active sites has emerged as a critical frontier in heterogeneous catalysis. However, conventional synthesis strategies struggle to reconcile high loading with ultrafine dispersion, often leading to nanoparticle aggregation and compromised stability. Herein, we present a coordination chemistry-driven strategy integrating the hard–soft acid–base principle with a water-etching process to synthesize ultrafine CuOx nanoparticles anchored on CeO2. By exploiting the differential coordination affinities of Ce3+ and Cu2+ with carboxyl ligands in a bimetallic BTC precursor, selective segregation during solvothermal synthesis was achieved. Ce3+ formed a stable framework with carboxyl groups, while Cu2+ underwent a hydrolysis-induced migration to surface defect sites. Regulating the Cu2+/Ce3+ ratio enabled precise control over CuOx dispersion, interfacial Cu–O–Ce bonding, and local structure. The optimized catalyst exhibited a remarkable Cu loading of 21.94% with high dispersion, lattice distortion, and enhanced metal–support interactions. Notably, the designed catalyst demonstrated exceptional stability under H2-rich streams, which achieved a CO conversion enhancement from 67.4 to 77.7% over 40 h through the interfacial stabilization of metastable Cu+-Ov-Ce4+ active configurations. Advanced characterization and density functional theory (DFT) calculations revealed that the enhanced interfacial Cu–O–Ce interactions and unsaturated coordinated CuOx species facilitated electron transfer, oxygen activation, and CO adsorption, synergistically boosting the catalytic performance via the Mars–van Krevelen mechanism. This work establishes a rational coordination chemistry-guided paradigm for designing high-performance catalysts with precisely engineered active sites.
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高影响因子
INORGANIC CHEMISTRY
·
2024
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IF 4.3
Dong Liu,Rundong Wu,Xianjie Wang,Runping Ye,Feiyang Hu,Xiaohan Chen,Tongtong Wang,Bingying Han,Zhang-Hui Lu,Gang Feng,Rongbin Zhang
It is crucial to eliminate CO emissions using non-noble catalysts. Cu-based catalysts have been widely applied in CO oxidation, but their activity and stability at low temperatures are still challenging. This study reports the preparation and application of an efficient copper-doped ceria electrospun fiber catalyst prepared by a facile electrospinning method. The obtained 10Cu–Ce fiber catalyst achieved complete CO oxidation at a temperature as low as 90 °C. However, a reference 10Cu/Ce catalyst prepared by the impregnation method needed 110 °C to achieve complete CO oxidation under identical reaction conditions. Asymmetric oxygen vacancies (ASOV) at the interface between copper and cerium were constructed, to effectively absorb gas molecules involved in the reaction, leading to the enhanced oxidation of CO. The exceptional ability of the 10Cu–Ce catalyst to adsorb CO is attributed to its unique structure and surface interaction phase Cu+-Ov-Ce3+, as demonstrated by a series of characterizations and DFT calculations. This novel approach of using electrospinning offers a promising technique for developing low-temperature and non-noble metal-based catalysts.
研究领域:
催化化学
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材料科学
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环境科学
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PubMed
高影响因子
Journal of Environmental Chemical Engineering
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2025
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IF 7.2
Yue Meng,Zhiling Huang,Di Liu,Bo Xie,Ying Guo,Shengjie Xia
In this paper, based on oxygen rich vacancies Bi 2 WO 6 -Ov@CoFe-LDHs heterojunction (BWO-Ov@LDHs), which can efficiently activate PS under visible light, BWO-Ov@LDHs/PS material system was fabricated for efficient degradation of tetracycline (TC). After 30 minutes photodegradation, the removal of TC by BWO-Ov@LDHs/PS reached 93.4 %, which is 2.9–3.1 times than that of pure PS and BWO-Ov@LDHs. Based on band structure, XPS result and theoretical calculations such as work function and differential charge density, it indicates that the Z-scheme heterojunction accelerates the transfer and conversion of electrons, and the activation of persulfate ions generates sulfate radicals, enhancing the photocatalytic performance, the variable valence state further strengthens the generation of sulfate radicals, and the tripartite synergy promotes the efficient photocatalytic degradation of TC. The results based on LC-MS provided the intermediate products and pathways of the degradation process, while toxicity analysis showed that the toxicity of intermediate products was lower.
研究领域:
环境科学
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材料科学
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高影响因子
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
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2021
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IF 6.514
Wen-Ying Shen,Chun-Peng Jia,An-Na Mo,Hong Liang,Zhen-Feng Chen
Three Cu(II) complexes of quinoline derivatives as cancer chemodynamic therapy agents were synthesized and characterized. These complexes were heavily taken up by cells and reacted with cellular glutathione (GSH) to reduce Cu 2+ to Fenton-like Cu + , which catalyzed endogenous H 2 O 2 to produce the highly toxic hydroxyl radicals (•OH) to kill cancer cells. Cu1 and Cu2 initiated CAT activity declines, mitochondrial membrane potential and ATP concentration decrease, mitochondrial Ca 2+ overload and ER stress response, leading to cell cycle arrest in sub-G1 and cancer cell caspase-dependent apoptosis . On account of the high GSH and H 2 O 2 specific properties of the tumor microenvironment , Cu1 and Cu2 exhibited higher in vitro anticancer activity and lower toxicity to normal cells. Cu1 and Cu2 efficiently inhibited tumor growth in the SK-OV-3 xenograft mouse model without obvious systemic toxicity.
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PubMed
高影响因子
Nanoscale
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2025
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IF 5.1
Chaojie Lyu,Jiarun Cheng,Chunyang Guan,Xueyan Li,Yongmao Zhao,Xudong Zhao,Yiming Liu
Cobalt molybdate (CoMoO4) is a potential material for the oxygen evolution reaction (OER) due to its stable crystal structure, strong redox capability, and abundant reserves. However, its poor electrical conductivity and high overpotential have limited its practical applications. In this study, the Ru@CoMoO4-Ov/NF composite was prepared by loading Ru nanoparticles onto CoMoO4 nanosheets and introducing oxygen vacancies (Ov). The interaction between Ru and CoMoO4 promotes electron transfer from Ru to Co, and this process is further enhanced by oxygen vacancies, leading to the formation of high-valence Run+. The high-valence Run+ strengthens the adsorption of oxygen-containing intermediates, thereby facilitating O-H bond cleavage, reducing the energy barrier for H2O decomposition, and improving OER performance. In 1 M KOH electrolyte, the catalyst exhibits an overpotential of only 249 mV at a current density of 10 mA cm-2, with a Tafel slope of 74.8 mV dec-1. When assembled into a two-electrode water-splitting system with FeP@CoP/NF, a current density of 10 mA cm-2 is achieved at a voltage of merely 1.54 V. Moreover, the catalyst maintains excellent catalytic stability even in a complex alkaline seawater electrolyte. This study provides important insights into the modification mechanism of CoMoO4-based catalysts.
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PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Zhichao Shang,Man Zhang,Jingjing Qu,Sanjith Udayakumar,Xintan Bai,Xiaohong Wang,Baojing Zhang,Jianzhong Wang,Farshid Pahlevani,Peizhong Feng
Chemical/electrochemical dealloying was applied to porous CoAl intermetallic (IMC) precursors synthesized via a rapid thermal explosion (TE) method, producing Co 3 O 4 (O V ) self-supported materials with rod-like, nano-flower, and honeycomb-like nanostructures. The investigation thoroughly explored the phase composition, exothermic behavior, precursor morphology, electrochemical characteristics of the dealloyed products, and the mechanism of oxygen vacancies that influence the performance of supercapacitors. The diffusion of intermediate phases governs the exothermic behavior and structural integrity of the CoAl IMC precursors, formatting a precursor with a porous material featuring a 3D microstructure. The effect of dealloying time, temperature and, applied potential on the nanostructure of the sample was examined, ultimately enabling the controlled synthesis of nano-flower Co 3 O 4 (O V ) in the dealloying process. The synthesized self-supported Co 3 O 4 (O V ) materials with a relatively high concentration of oxygen vacancies and a high specific surface area (36.69 m²/g). The materials showed high capacitance (11.25 F/cm 2 at 10 mA/cm 2 ) and exceptional cyclic stability (the decay rate per cycle is 0.013 % at 20 mA/cm 2 after 2000 cycles). DFT simulations demonstrated that the O V creates additional unsaturated coordination sites, enhancing the storage capacity by facilitating ion insertion and extraction, thus significantly boosting the specific capacity.
研究领域:
材料科学
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电化学
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能源存储
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高影响因子
Journal of Cleaner Production
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2022
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IF 11.072
Xiuyan Wang,Bingdi Wang,Shengyan Yin,Mingwei Xu,Lixue Yang,Hang Sun
Low solubility and slow diffusion of nitrogen (N 2 ) in water are significant impediments for enhancing the efficiency of fixation nitrogen into ammonia (NH 3 ). Herein, we have prepared bio-inspired hierarchical assembly of carbonized loofah sponge@BiOBr-OV/Au (CL@BiOBr-OV/Au) to improve diffusion of nitrogen by immobilization of hydrophilic BiOBr-OV/Au onto hydrophobic CL sponge. The hydrophobic CL sponge provides an optimized directional channel for N 2 diffuse to the triphase interface N 2 (gas)-H 2 O (liquid)-BiOBr-OV/Au (solid), which supplies generous N 2 for the photocatalytic reaction and replaces the slow diffusion of N 2 through the liquid phase . Continuous delivery of N 2 can effectively capture generated electrons , thereby preventing the recombination of generated electron-hole and promoting N 2 activation. The modification of AuNPs can broaden the photoresponse range of BiOBr-OV, increase oxygen vacancies concentration and enhance N 2 adsorption and activation. CL@BiOBr-OV/Au shows an impressive in nitrogen fixation performance with high selectivity and recyclability of 2.64 mmol·g cat −1 ·h −1 , that is 10.2 and 8.0 times compared to CL@BiOBr-OV and BiOBr-OV/Au, respectively. Our work affords a convenient method for the construction of bio-inspired triphase catalysts with a directional N 2 transport channel to enhance the efficiency of nitrogen fixation, which also holds great promise for the application in other reactions involving gas consumption.
研究领域:
材料科学
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催化
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环境科学
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化学工程
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高影响因子
ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Fanhui Liao,Weibin Liang,Meixian Li,Donghai Xu,Le Yang
Selective hydrogenation of carboxylic acids to alcohols remains a challenge due to the requirement of synergistic multiple active sites for H2 activation, reactant adsorption, and selective C–O bond scission. Here, we construct a series of Co–Al metal–metal oxide (MMO) catalysts via the hydrogen-induced reduction of layered double hydroxide (LDH) precursors with tunable Co/Al ratios. The optimal Co4Al1-MMO catalyst exhibits highly dispersed Co0 nanoparticles alongside abundant oxygen vacancies (Ov-Co). The Co0/Ov-Co dual sites synergistically promote H2 dissociation and carbonyl oxygen C=O bond activation, while moderate lattice oxygen stabilizes the metastable structure. Under mild conditions (180 °C, 2 MPa of H2, 3 h), the catalyst achieves 100% conversion of octanoic acid with 99% alcohol selectivity, outperforming state-of-the-art noble-metal systems. This work provides a general strategy for engineering cooperative metallic/defective sites in nonprecious MMO catalysts for selective hydrogenation reactions.
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高影响因子
FUEL
·
2025
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IF 7.5
Shijie Ma,Hangcheng Song,Jun Chen,Shuyan Yu,Hongyu Zhao
Biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dihydroxymethylfuran (DHMF) is a pivotal process in biomass valorization, however, it is hindered by the high cost of noble metal catalysts and environmental hazards posed by toxic copper-chromium systems. Herein, we report an unexpected discovery that naturally occurring Fe-Ti impurities in kaolinite act as a highly efficient heterogeneous catalyst for this reaction, challenging the conventional notion that impurities are detrimental to catalytic performance. Through hydrothermal synthesis and controlled reduction, Fe species are highly dispersed on the TiO 2 rutile surface, forming a synergistic Fe 2+ -oxygen vacancy-Ti 4+ (Fe 2+ -O v –Ti 4+ ) interface. The catalyst exhibits outstanding activity and selectivity under mild conditions (50 °C, 0.6 MPa H 2 ), achieving 97.6 % HMF conversion and 93.3 % DHMF selectivity, significantly outperforming catalysts based on kaolin and pure TiO 2 . Kinetic analysis reveals an apparent activation energy of 50.14 kJ/mol and a near first-order dependence on HMF concentration. Combined DFT calculations and in situ DRIFTS spectra confirm that the Fe 2+ -O v interface facilitates the adsorption of the HMF aldehyde group (adsorption energy −0.56 eV) and lowers the energy barrier for H 2 dissociation to 0.06 eV, enabling highly selective C=O hydrogenation. Moreover, the reaction benefits from the strong polarity of water and the hydrogen-bonding capacity, which further enhances catalytic performance. The catalyst retains over 90 % activity after 10 cycles, demonstrating excellent stability. This work not only provides a sustainable route for high-value utilization of kaolin-associated metal impurities, but also offers theoretical insights into the rational design of non-precious metal catalysts for biomass transformation.
研究领域:
催化化学
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生物质能源
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材料科学
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环境友好化学
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表面科学
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高影响因子
Nano Today
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2023
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IF 17.4
Chen Xu,Keman Cheng,Xinwei Wang,Jingjing Liu,Jie Liang,Guangna Liu,Yichao Lu,Ming Tang,Dingfei Qian,Liting Chen,Zhenguo Cheng,Zhenning Wang,Xiao Zhao,Funan Liu
Through eliciting direct oncolysis, oncolytic viruses (OVs) induce release of tumor proteins, some of which can act as antigens to evoke an antitumor adaptive immune response. However, the poor immunogenicity and utilization efficiency of soluble tumor antigens limit the strength of the activated adaptive immune response and the clinical outcome of OVs. In this study, we found intratumoral injection of oncolytic virus, some of which was drained to the peritumoral lymph nodes. we proposed a strategy to modify oncolytic viruses (OVs) with antigen catchers (polyethylene glycol-linked maleimide) which efficiently capture tumor-derived proteins produced by oncolysis without diminishing its bioactivity of infecting tumor cells, then furtherly triggering enhanced antitumor adaptive immune response. In addition, the surface PEG layer protected AD 11 -Mal from the pre-exiting anti-AD 11 immunity to expand the applicability of AD 11 -Mal. Finally, we combined AD 11 -Mal with an indoleamine 2, 3-dioxygenase (IDO) inhibitor 1-methyl-tryptophan (1-MT) to overcome the local negative feedback in tumor immune microenvironment , which combinational regimen induced the long-lasting immune memory to inhibit tumor recurrence. In summary, our strategy greatly enhances the tumor antigen-specific adaptive immunity induced by OV therapy even in the presence of pre-exiting anti-OV immunity, which maybe promising for the development of next-generation OVs.
研究领域:
癌症免疫治疗
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分子生物学
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肿瘤学
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免疫学
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高影响因子
FUEL
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2025
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IF 7.5
Yongpeng Ma,Jianghui Du,Yifei Wu,Haobing Yan,Ruiqi Liu,Xiaojing Zhang,Hongzhong Zhang,Liming Zhou,Wenjun Huang
Among the diverse pollutants emitted from coal-fired and non-ferrous metal smelting flue gas, Hg 0 and CO have emerged as globally concerning environmental pollutants. However, the simultaneous abatement of multiple pollutants remains a critical challenge to be addressed. In this study, cobalt nanoclusters (Co NCs) were anchored on the terminal oxygen of Ti-O on Ti 3 C 2 MXene and formed asymmetric oxygen vacancies Co-Ov-Ti via a one-step hydrothermal method, yielding Co NCs/Ti 3 C 2 MXene with a morphology of hierarchical nanosheet-assembled spheres for Hg 0 and CO catalytic oxidation. Co NCs/Ti 3 C 2 MXene exhibited excellent 44 % and 52 % of Hg 0 and CO simultaneous removal efficiency at the optimal temperature of 250 °C, respectively. DFT calculations combined with energy barrier modeling were employed to investigate the reaction pathways and energy variations during the catalytic oxidation of Hg 0 and CO. Specifically, Hg 0 oxidation follows the Eley-Rideal mechanism, with a rate-determining energy barrier of 2.11 eV, while CO oxidation adheres to the Langmuir-Hinshelwood mechanism, featuring a rate-determining barrier of 0.17 eV. In the co-catalytic oxidation process, competitive adsorption between Hg 0 and CO was observed, primarily manifested as competition for Ov on the catalyst surface. This study provides a novel strategy for the synergistic control of multi-pollutants in industrial flue gas.
研究领域:
环境催化
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材料科学
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大气污染控制
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物理化学
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纳米材料
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高影响因子
危险品化学品经营许可证（带存储）