Nanoscale
·
2024
·Vol. 16
·期 10
·5215-5221
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IF 5.8
Yangdong Zhou,Junda Chen,Zhiyin Huang,Yuqin Peng,Lixin Xing,Chunmei Tang,Ning Wang,Ling Meng,Mingjie Wu,Lei Du,Siyu Ye
The cathodic oxygen reduction reaction (ORR) has been continuously attracting worldwide interest due to the increasing popularity of proton exchange membrane (PEM) fuel cells. So far, various Pt-group metal (PGM) or PGM-free catalysts have been developed to facilitate the ORR. However, there is still a gap to achieve the expected goals as proposed by the U.S. Department of Energy (DoE). Recently, PGM-free@PGM hybrid catalysts, such as the M/N/C@PtM catalyst, have achieved the milestones of oxygen reduction, as reviewed in our recent work. It is, nevertheless, still challenging to unravel the underlying structure–property relationships. Here, by applying different Pt/Co ratios, a series of Co/N/C@PtxCo catalysts are synthesized. Interestingly, the ORR activity and stability are not linear with the Pt content, but show a volcano-like curve with increased Pt usage. This relationship has been deeply unraveled to be closely related to the contents of pyrrolic N, pyridinic N, and graphitized carbon in catalysts. This work provides guidelines to rationally design the coupled PGM-free@PGM catalysts toward the ORR by appropriate surface engineering.
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JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Jihai Zhao,Qi Wang,Yaowen Wang,Xinbo Li,Chang Liu,Taotao Huang,Liping Li,Guangshe Li
The spin state of transition metal ions, specifically controlled by the electrons in antibonding orbital, is recognized as a descriptor for heterogeneous catalysts. However, the influence of spin state on the adsorption of CO molecular with two electrons in the highest occupied molecular orbital, has been overlooked. In this work, the Co 2+ spin states in multicomponent rock-salt oxides are regulated by increasing configurational entropy, demonstrating the impact of Co 2+ spin states on CO adsorption. The CO catalytic oxidation activity of as-synthesized rock-salt oxides exhibits a volcano-shaped relationship with the ratio of Co 2+ in high spin state to Co 2+ in low spin state. Mg 0.33 Co 0.33 Ni 0.33 O with this spin state ratio of 7.5 has the largest negative adsorption energy to CO molecular and exhibits the best catalytic activity. The findings on the relationship between the spin state of transition metal ions and reactant adsorption can contribute to the understanding of catalytic activity at the electronic level.
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CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Penggang Li,Ping Zhang,Aishu Li,Lin Yu,Mengying Si,Qi Liao,Zhihui Yang,Weichun Yang
Understanding the formation of uranyl-arsenate compounds (M(UO 2 ) 2 (AsO 4 ) 2 ·nH 2 O, M represents divalent metallic cations) is of great importance in controlling the mobility and fate of uranium (U) and arsenic (As) in the natural environment. Phosphate is a ubiquitous coexisting ion with properties similar to arsenate and can complex with uranyl to form uranyl phosphate compounds, thus potentially affecting the formation of uranyl-arsenate compounds. Herein, the effect of phosphate, on the immobilization of uranyl, arsenate and divalent metallic cations (e.g., Fe 2+ , Mg 2+ , Ni 2+ , Cu 2+ ) was explored. Surprisingly, the presence of phosphate promoted the immobilization of uranyl arsenate with the divalent metallic cations under acidic conditions. For example, at pH 3.0, the immobilization efficiency of uranyl and arsenate in the uranyl-arsenate-Fe 2+ system increased from 20.6 % and 18.6 % to 82.6 % and 52.2 %, respectively. Moreover, the chemical stability of the formed uranyl arsenate-bearing compounds in the presence of phosphate is significantly improved, and the TCLP leachability of As and U decreased by 81 % and 97 %, respectively. The experimental results illustrated that with PO 4 3- served as a proton acceptor, uranyl and arsenate species were changed and more metallic cations participate in immobilization. Gibbs free energy and Gibbs free energies change also illustrated that the formation of Fe(UO 2 ) 2 (AsO 4 ) 2 ·5H 2 O was relatively thermodynamically favorable in the presence of phosphate. The results of thermodynamic calculations could account for the enhancement effects of phosphate on immobilization of uranyl arsenate. The findings have important implications for the mobility and fate of U and As and the solution of their co-contamination, especially in acidic environments.
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ACS Applied Nano Materials
·
2025
·
IF 5.5
Changsong Chen,Xusheng Yang,Zhiyong Fu,Le Zhou,Bin Xu,Kaiming Zhang,Shengbin Zhou,Limei Zhou,Weidong Jiang
Traditional hydrogenation requires noble metal catalysts and harsh conditions. To overcome these intrinsic drawbacks, herein, sulfur-doped Co3O4–CuO/CNS bicomponent nanocomposites were prepared using S-modified chitosan (CNS) as a template via the precipitation method. The experimental results demonstrated that the incorporation of sulfur (S) significantly enhanced the synergistic effect of the Cu–Co-based bimetallic system, thereby improving catalytic activity. Notably, Co3O4–CuO/CNS-10 exhibited remarkable catalytic performance in the hydrolytic dehydrogenation of sodium borohydride, achieving a hydrogen generation rate (HGR) of 357.9 mL·min–1·g–1cat. Furthermore, Co3O4–CuO/CNS effectively catalyzed the tandem hydrogenation reduction of m-nitrobenzene (m-CNB) to m-nitroaniline (m-CAN) in the presence of sodium borohydride (NaBH4), as evidenced by an m-CAN yield of up to 99.80% under highly mild conditions. Also, Co3O4–CuO/CNS-10 displayed high chemoselectivity and regioselectivity for the reduction of various aromatic nitro compounds containing potential reactive functional groups. The doping of sulfur promotes the bimetallic Cu–Co synergistic effects accompanied by the increases of the Co2+/Co3+ ratio and enriches oxygen vacancy defects on the surface, thereby enhancing the catalytic activity of the screened heterogeneous catalyst. This work highlights the key role of sulfur and provides an innovative strategy for elevating the catalytic reactivity of bimetallic nanocatalysts.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2021
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IF 19.503
Ming Zhu,Daqin Guan,Zhiwei Hu,Hong-Ji Lin,Chien-Te Chen,Hwo-Shuenn Sheu,Shaobin Wang,Jing Zhou,Wei Zhou,Zongping Shao
Synergistic effects are often used in catalyst design for many environmental/energy applications, however, the mechanism and a molecular-level structure to exert maximal synergy effects in catalyzing advanced oxidation processes (AOPs) in wastewater remediation are still unknown. Here, by designing a model perovskite family R BaCo 2 O 6- δ ( R = lanthanides) with Co 4+ in octahedral coordination (Co4+ oct) and Co 3+ in pyramidal coordination (Co3+ pyr), we ambitiously confirm the unique synergy of unsaturated (Co3+ pyr) and metallic (Co4+ oct) Co sites for efficient peroxymonosulfate (PMS) activation. Combined X-ray adsorption spectra and theoretical calculations strongly demonstrate that Co3+ pyr and Co4+ oct synergistically contribute to PMS adsorption and O O bond cleavage, and facilitate Co 3+ /Co 4+ redox cycle for radical generation. With appropriate ratio and ordered distribution of Co3+ pyr/Co4+ oct, the Gd 0.5 La 0.5 BaCo 2 O 5.75 exhibits remarkable catalytic activity for pollutant degradation, outperforming all previously reported Co 4+ -related oxides. This work may inspire rational design of efficient metal oxide catalysts.
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ADVANCED FUNCTIONAL MATERIALS
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2025
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IF 19
Huajie Zhong,Junhui Wang,Bin Zhang,Yangyang Liu,Zeyu Gong,Xinzhe Xiao,Jiaxing Yu,Yu Hou,Yuan Tao,Huangsheng Yang,Qi Fu,Jiating Zheng,Pengfei Wang,Gangfeng Ouyang
Carbon-supported single-atom catalysts (CS-SACs) have attracted tremendous attention in environmental remediation fields, however, the role of the ubiquitously existing carbon defects on the support in regulating the electronic structure of active metal sites has long been overlooked. Herein, a selective pyridinic N etching strategy is proposed to controllably fabricate specific pentagon defects in the carbon supports anchored with Co-N 4 sites. Theoretical and experimental results reveal that the pentagon defects can induce upward shifting of the Co d-band center and increase the electron density in the dxz and dz 2 orbitals, indicating its indispensable role in regulating the electronic structure of the metal center. As a result, efficient electron transfer is realized between the Co atom and peroxymonsulfate (PMS). Moreover, the energy barriers for crucial oxygen intermediate are reduced, which facilitates the generation of singlet oxygen ( 1 O 2 ). Consequently, the Co-N 4 catalyst with pentagon defects (C5-Co-N 4 ) achieved a remarkable TOF value (9.37 min −1 ) in a Fenton-like reaction, surpassing the state-of-the-art single-atom catalysts reported so far. This work not only provides a strategy to controllably fabricate specific defects in CS-SACs but also deepens the fundamental understanding on how pentagon defects regulate the electron structure and catalytic performance of metal-N 4 sites.
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ADVANCED MATERIALS
·
2025
·
IF 26.8
Anquan Zhu,Heng Liu,Lulu Qiao,Bin Liu,Kunlun Liu,Chuhao Luan,Kai Liu,Yin Zhou,Dewu Lin,Guoqiang Gan,Jiapei Li,Guo Hong,Wenjun Zhang
The electrochemical nitrate reduction reaction (eNO 3 RR) is widely recognized as a promising strategy for sustainable ammonia production and supporting the nitrogen cycle. However, its advancement is impeded by complex behavior of reaction intermediates and the inevitable reconstruction of precatalysts. To address these challenges, the generation and utilization of active hydrogen (*H) are strategically managed by tailoring the RuO 2 /Co 3 O 4 precatalyst and optimizing the electrolyte composition (OH − and NO 3 − concentration), thereby selectively enhancing ammonia formation. Consequently, the in situ reconstructed RuO 2 /Co(OH) 2 catalyst achieves an impressive ammonia yield of 35.9 ± 0.9 mg h −1 cm −2 and a Faradaic efficiency (FE) of 98.1 ± 2.6% at −0.3 V versus RHE. Furthermore, the catalyst shows significant potential for applications in nitrate-rich wastewater treatment and rechargeable Zn-NO 3 − batteries, maintaining stable operation for over 260 hours at 1 mA cm −2 with only a 6 mV increase in the potential window. Mechanistic studies reveal that electron-rich RuO 2 facilitates *H generation through water dissociation, which subsequently migrates to Co(OH) 2 to hydrogenate nitrogenous intermediates, selectively producing ammonia. This study highlights the importance of designing efficient catalytic systems that address both precatalyst reconstruction and the complexities of reactant and intermediate conversion in electrolytes, which are essential for managing the intricate electron and proton transfer processes involved in eNO 3 RR.
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APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Yi-Hong Yu,Xin Cui,Yi-Meng Hong,Gao-Wu Qin,Song Li
Incorporating electrochemical CO 2 reduction (ECR) that produces CO-rich syngas into the workflow of steelmaking presents a promising strategy to neutralize the steelmaking industry. Herein, we develop a highly efficient and stable Ag nanowires with surface CeO 2 armors (CeO 2 /AgNWs) as ECR electrocatalyst for syngas production. The engineered CeO 2 -Ag interface facilitates CO 2 -to-CO conversion by lowering the energy barrier for *COOH intermediate formation through synergistic electronic effects. At an industrially relevant current density of −251.3 mA cm −2 , the CeO 2 /AgNWs generate CO-rich syngas by co-electrolysis of CO 2 and H 2 O, with a high Faradaic efficiency (FE) of 92.1 % for CO. Techno-economic analysis (TEA) reveals that integrating the CeO 2 /AgNWs-driven ECR into existing steelmaking workflows can potentially reduce CO 2 emissions by 83 % and elevate the renewable energy utilization to ∼91.4 %, unlocking new possibilities for achieving carbon neutrality in the steel industry.
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NEW JOURNAL OF CHEMISTRY
·
2025
·
IF 2.5
Xuan Liu,Jie Chao,Feifei Guo,Liangliang Chang,Zengzhe Xi
To address rapid carrier recombination and low magnetic separation efficiency in piezocatalysis, Gd/Ni co-doped BiFeO3 nanoparticles were synthesized via a sol–gel method. Rietveld refinement confirmed lattice distortion and secondary phase formation at high doping levels. Gd/Ni doping induces a phase transition in BFO from rhombohedral to orthorhombic, with the Pnma proportion reaching 84.15% at x = 0.09. Gd/Ni co-doping induced 12.7% oxygen vacancy concentration, suppressing electron–hole recombination, while enhanced Dzyaloshinskii–Moriya interaction increased saturation magnetization by 17.85-fold (magnetic recovery > 95%). The optimized sample (x = 0.09) achieved 80.94% ofloxacin degradation in 120 min (twice that of pristine BiFeO3), retaining 71.53% efficiency after 4 cycles. Radical trapping and EPR identified ˙OH and ˙O2− as dominant species, revealing a ferroelectric–piezoelectric synergistic mechanism. This work provides a strategy for designing magnetically recoverable piezocatalysts for complex wastewater treatment.
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APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Hang Xu,Lijuan Wang,Zhuoran Tian,Jingru Geng,Jinsheng Liang
Designing efficient photocatalysts is crucial for enhancing photocatalytic performance, with the separation efficiency of photogenerated charge carriers being a key factor, the improvement of this performance can significantly enhance antibacterial efficiency. To address the limitations of traditional bismuth oxybromide (BiOBr) photocatalysts, this study synthesized visible-light-driven Al/Cu co-doped BiOBr (2ACBB) microspheres via a solvothermal method. Dual metal doping synergistically modifies the band structure, introducing oxygen vacancies that narrow the bandgap (2.69 eV vs. 2.80 eV) while enhancing visible-light absorption and charge separation efficiency. Optimized 2ACBB exhibits a high surface area (27.64 m 2 /g) and demonstrates 3.2-fold greater photocurrent response than pristine BiOBr. EPR analysis reveals superoxide radicals ( · O 2 - ) and electrons as dominant reactive species, enabling exceptional antibacterial performance (99.99 % S. aureus and 97.99 % E. coli inactivation within 40 min). Mechanistic studies confirm that hierarchical architecture promotes bacterial adsorption and light harvesting, while generated · O 2 - and e − disrupt membrane integrity and metabolic processes. This work on the enhanced antimicrobial properties of metal ion-doped photocatalytic materials provides a perspective.
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TRIBOLOGY INTERNATIONAL
·
2025
·
IF 6.9
Baokai Zhang,Yanming Wang,Xian-Qiang Pei,Xiaoliang Zhang,Gai Zhao,Qihua Wang,Tingmei Wang
Solvent-free nanofluids have attracted increasing attention in tribological applications due to their distinctive load-bearing lubrication mechanisms, which arise from the synergistic interaction between its surrounding corona/canopy structures. In this study, a nanofluid was developed by incorporating N,S-co-doped carbon dots (N,S-CDs) and Jeffamine M2070 into polyimide (PI) matrix. This composite reduced the COF by 61 % (0.15 ± 0.01) and the wear rate by 95 % (3 ± 0.1643) × 10 −6 mm 3 /N·m compared to pure PI. N,S-CDs adsorbed onto friction surfaces via -NH 2 and -COOH groups, enhancing interfacial bonding and raising peak interface temperature by 126 K. This promoted PI fragment graphitization and robust tribofilms formation. M2070 further smoothed the interface by filling voids. The work proposes a “core-resin interface with casing” strategy for tribological materials in high-load, precision applications.
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Nature Catalysis
·
2023
·
IF 37.8
Sun Kai,Dong Juncai,Sun Hao,Wang Xingdong,Fang Jinjie,Zhuang Zhongbin,Tian Shubo,Sun Xiaoming
Metal-nitrogen-doped carbon (M-N-C) catalysts are promising platinum group metals alternatives for fuel cell cathodes; however, their randomly formed, unpredictable coordinations complicate any structure–property investigation and lead to low active site density. Here we achieve dense and well-defined cobalt sites on the surfaces of Co(CN) 3 microcrystals, which are identified by single-crystal X-ray diffraction and X-ray absorption spectroscopy. In situ infrared spectroscopy and density functional theory calculations elucidate that the high oxygen reduction reaction performance (half-wave potential is 0.90 V versus RHE) of the cubic Co(CN) 3 is due to its tailored coordination environment that optimizes *OH desorption. The cyanide linkage with minimized spacing between cobalt atoms maximizes active sites’ spatial density, which boosts the anion-exchange membrane fuel cell peak power density to 1.67 W cm −2 . The microcrystals with well-defined coordination structures can be used as Co-N-C analogues for their structure–property relationship investigations.
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