IONICS
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2023
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IF 2.8
Li Wei,Zhao Yi,Zhang Chunyan,Kang Juanxue,Tang Qinyuan,Liu Yongfei,Yang Lin,Yuan Shutang
The production of hydrogen peroxide (H 2 O 2 ) by 2-electron oxygen reduction reaction (ORR) in acidic electrolytes is a promising alternative to the existing anthraquinone process. However, the development of cost-effective catalysts with high activity for H 2 O 2 electrosynthesis remains a great challenge. Here, we report a cobalt-nitrogen-carbon catalyst in which cobalt single atoms are supported on carbon black (Co-N-CB) for the electrosynthesis of H 2 O 2 in an acid medium. The prepared Co-N-CB shows high activity for O 2 reduction into H 2 O 2 with an average selectivity of 80.6% over a wide potential range of 0.1–0.7 V vs. RHE in 0.1 M HClO 4 electrolytes. We found that (i) the Co single atoms are the active sites of 2-electron ORR; (ii) a catalyst for efficient H 2 O 2 production by O 2 reduction should achieve a good balance between high ORR activity and H 2 O 2 selectivity. Using Co-N-CB as a cathodic catalyst, the electrochemical device could electrosynthesize H 2 O 2 directly from H 2 and O 2 with a high productivity of 291.0 mol kg cat −1 h −1 . Our work provides a flexible way to prepare affordable catalysts for efficient H 2 O 2 electrosynthesis.
研究领域:
材料科学
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催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Jinghang Chen,Yuqi Ren,Yiwei Fu,Yitao Si,Jie Huang,Jiancheng Zhou,Maochang Liu,Lunbo Duan,Naixu Li
We report a solvothermal method for the synthesis of an oxygen vacancy-enriched ZrO2 photocatalyst with Co single atoms and Ni clusters immobilized on the surface. This catalyst presents superior performance for the reduction of CO2 in H2O vapor, with a CO yield reaching 663.84 μmol g–1 h–1 and a selectivity of 99.52%. The total solar-to-chemical energy conversion efficiency is up to 0.372‰, which is among the highest reported values. The success, on one hand, depends on the Co single atoms and Ni clusters for both extended spectrum absorption and serving as dual-active centers for CO2 reduction and H2O dissociation, respectively; on the other hand, this is attributed to the enhanced photoelectric and thermal effect induced by concentrated solar irradiation. We demonstrate that an intermediate impurity state is formed by the hybridization of the d-orbital of single-atom Co with the molecular orbital of H2O, enabling visible-light-driven excitation over the catalyst. In addition, Ni clusters play a crucial role in altering the adsorption configuration of CO2, with the localized surface plasmon resonance effect enhancing the activation and dissociation of CO2 induced by visible–near-infrared light. This study provides valuable insights into the synergistic effect of the dual cocatalyst toward both efficient photothermal coupling and surface redox reactions for solar CO2 reduction.
研究领域:
材料科学
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环境科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Baoyu Wang,Mingrui Li,Songdang Zhang,Hongguo Wu,Yuhe Liao,Hu Li
Finite size effect is closely correlated with heterogeneous catalytic activity and selectivity as reducing the metal to a few nanometers, but may suffer from deficient active sites for cascade reactions. Here, a type of dual-size heterogeneous N-doped cobalt catalysts (Co SAs-NPs /NC(n)) with the coexistence of Co single-atoms (Co-SAs) and Co nanoparticles (Co-NPs) were prepared for efficient synthesis of benzimidazoles (up to 91% yield) from 2-nitroanilines and bio-based alcohols via cascade hydrogen transfer-dehydrogenative cyclization. Experimental results and density functional theory calculations suggested that the bio-alcohol dehydrogenation mainly occurs at Co-SAs sites, while Co-NPs sites remarkably facilitate the subsequent reduction of nitro species, indicating the synergistic effect between Co-SAs and Co-NPs in the coupled hydrogen transfer process. The Co SAs-NPs /NC(0.25) catalyst can be recycled and applied to a wide range of substrates (28 examples). This catalytic approach based on the metal size effect opens a new route for the direct upgrading of biomass feedstocks involving multiple reactions.
研究领域:
催化化学
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材料科学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
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IF 17.7
Liwen Guo,Dao Shi,Tianjun Zhang,Yanhang Ma,Guodong Qi,Jun Xu,Qiming Sun
Propane dehydrogenation (PDH) has emerged as a key on-purpose technology for the production of propylene, but it often depends on toxic chromium and expensive platinum catalysts, highlighting the need for environmentally friendly and cost-effective alternatives. In this study, we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co 1 O 3 H x structure by regulating silanol nests in purely siliceous Beta zeolites. Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity. Additionally, the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles. Notably, the optimized Co 0.3% /deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol C3H6 g cat –1 h –1 , with an exceptional propylene selectivity of 99.1% at 550 °C. Moreover, the Co 0.3% /deAl-meso-Beta catalyst demonstrated excellent stability, with negligible deactivation after 5 consecutive regeneration cycles. This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites, providing valuable insights for the design of high-activity, high-stability, and low-cost PDH catalysts.
研究领域:
催化化学
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材料科学
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能源化工
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
·
IF 13.3
Heming Qi,Xingling Wang,Ming Lei,Wenyu Fan,Shuangshuang Huang,Lihua Zhu,Heqing Tang
Non-precious catalysts are a potential candidate for highly efficient conversion of nitrobenzene to aniline if these catalysts can work under mild conditions. Here, we developed a catalyst (Co (SA+NPs) -C/N) by depositing Co species on nitrogen-doped carbon support with a pyrolysis route under a nitrogen atmosphere. As two forms of Co species, both single atom cobalt (Co (SA) ) and cobalt nanoparticles (Co (NPs) ) were distributed on the surface of the catalyst particles. These two forms of Co species provided a synergistic effect (dual-sites effect) on the hydrogenation of nitrobenzene to aniline. Using water as a solvent, the optimized Co (SA+NPs) -C/N catalyst yielded a full conversion of nitrobenzene into aniline at room temperature within 2.5 min in the presence of NaBH 4 with a molar ratio of –NO 2 : NaBH 4 = 1: 3. The observed catalytic activity of Co (SA+NPs) -C/N was much higher than that of the catalyst with only single atom cobalt (Co (SA) -C/N) or only cobalt nanoparticles (Co (NPs) -C/N). The synergistic dual-sites effect is assigned as that Co nanoparticle sites contribute enough sites for the adsorption of nitrobenzene and its intermediates, while the dispersed Co atom sites boost the dissociation of NaBH 4 molecules to active H atoms. The Co (SA+NPs) -C/N catalyst was able to smoothly work at a wide temperature range of 15-45°C, being highly stable with a recycling number of at least ten. This work not only opens up a new approach for the transfer hydrogenation of nitrobenzene, but also deepens the knowledge on their hydrogenation mechanism.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
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2023
·
IF 8.6
Wenquan Wang,Xiaohui Deng,Zhengbin Tian,De-Chang Li,Guang-Hui Wang
Although the synergy between single atom sites (SAs) and nanoparticles (NPs) can enhance the oxygen reduction performance, current synthetic strategies are not able to precisely control the distribution of SAs/NPs or the size of NPs under high metal loading, undesirably limiting the overall performance. Herein, we report that the pyrolysis of nanosized zeolitic imidazolate frameworks (ZIF-67) that are preconfined in the pores of mesoporous carbon (MC) can produce Co SAs and NPs (mean size of 4.3 nm at 15 wt % loadings) in close proximity to each other. As the movement of finely dispersed ZIF-67 is restricted by the pore-confinement configuration, the pyrolysis of spatially isolated ZIF-67 units can produce abundant Co–N4 sites distributed in the first or second graphitic shell encapsulating the NPs. Benefitting from the high density of active sites, the maximized synergetic interaction of SAs/NPs, and the rich mesoporosity of MC, Co-SAs/NPs@MC exhibits a half-wave potential (E1/2) of 0.91 V and excellent durability under alkaline conditions, outperforming commercial Pt/C and most reported counterparts. Control experiments combined with density functional theory calculations evidence that the presence of Co NPs is essential to optimize the adsorption of intermediates on the intimately coupled, catalytically active Co–N4 sites toward ORR. Moreover, it is revealed that the distance between Co SAs and NPs is critical for superior activity. As controlled fabrication of SA/NP hybrid catalysts is desired, the pore-confinement methodology reported herein and the advantages demonstrated by ORR are expected to guide the design of other functional catalysts.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
·
IF 19
Xue Lu,Fei Xiang,Shaoyi Li,Wenke Liu,Yiwen Zeng,Ximei Fan,Jian Yang,Andrea Fratalocchi
Electrocatalysts combining metal single-atom and nanocluster synergy are promising alternatives to platinum-based catalysts for oxygen reduction reaction (ORR). However, controllable synthesis of such catalysts with high ORR performance remains challenging due to metal atom aggregation into large nanoparticles. Here, a hydrogen-bond network confinement approach to construct Co nanocluster and Co-N x -C moiety coexisting active sites on nitrogen-doped porous carbon for highly active and long-term stable ORR is reported. The optimized Co@Co-N-C catalyst exhibits a half-wave potential (E 1/2 ) of 0.92 V versus RHE and a limiting current density (J L ) of 6.02 mA cm −2 for ORR, presenting a 40 mV positive shift in E 1/2 than the competitor with the highest J L and 15.7% improvement in J L over the catalyst with the most positive E 1/2 . The enhanced catalytic performance originates from the synergy between Co nanocluster and Co-N x -C moieties, which modulates the electronic structure of the Co-based active sites and improves the electrochemically active surface area. The zinc-air battery assembled with Co@Co-N-C catalyst delivers a specific capacity of 870 mAh g −1 and a maximum discharge power density of 210 mW cm −2 , representing ≈52% improvement over Pt/C-based devices. This hydrogen-bond-assisted synthesis strategy opens pathways for designing high-performing catalysts in diversified fields beyond ORR, including water splitting, CO 2 reduction, and nitrogen reduction.
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
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Tongze Sun,Yansong Liu,Jiage Li,Yanan Zhang,Bowen Zhao,Mingyu Li,Chongjun Zhang,Mingxin Huo,Jingjing Jiang,Shuangshi Dong
Decreasing spin state of cobalt to reduce the redox energy barrier of peroxymonosulfate has been challenging. Herein, we constructed asymmetric coordination of Co−BN 3 to decrease spin state of cobalt from high to medium. The developed medium-spin cobalt-mediated Fenton-like system had a carbamazepine degradation rate constant of 0.815 min −1 and removed 58.0% of chemical oxygen demand, 52% of total phosphorus, 69% of total nitrogen and 85% of ammonia nitrogen from the hospital wastewater. This was attributed to that the medium-spin cobalt formed by the construction of asymmetric Co−BN 3 , enhancing the electrons absorption and donation from dz 2 and dx 2 -dy 2 orbitals to PMS, achieving the reduction in redox energy barrier of peroxymonosulfate for the generation of sulfate radical and singlet oxygen. This work provided a new perspective to develop efficient spin-induced synergistic oxidation Fenton-like water treatment technology.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
Materials Today Chemistry
·
2022
·
IF 7.613
J. Chen,G. Li,N. Lu,H. Lin,S. Zhou,F. Liu
Covalent triazine frameworks (CTFs) show great potential in photocatalytic fields, while their practical efficiency is still limited due to rapid charge recombination. Here we report a nanospatial separation strategy for photoinduced electron-hole pairs of CTF-1 nanosheets via single-atom Co using facile pyrolysis and phosphorization to form stable Co–N 3 (≈1.60 Å) architecture. HAADF-STEM image demonstrates Co atoms are uniformly dispersed onto ultrathin CTF-1. The local structure surrounding and chemical valent state of Co are systematically investigated by Fourier-transformed EXAFS and K-edge XANES , respectively. Co single atoms as oxidation centers can capture holes transferred from CTF-1, thus resulting in narrow bandgap and improved photo-exciton dissociation in the two-dimensional (2D) direction. The obtained Co/CTF-1 exhibits excellent efficiency of 99.9% for pollutant photodegradation, far outperforming that of pristine CTF-1 (68.8%). Nanospatial separation endows Co/CTF-1 with various micropollution removal capabilities, outstanding cyclic stability, and a widely effective pH range (1.0–11.0) under visible light. Furthermore, active oxidating radicals of h + and •O 2 − are dominant in photocatalytic degradation for various organic contaminants. This study motivates the atomic design and fabrication of 2D photocatalysts with excellent charge nanospatial separation.
研究领域:
材料科学
·
环境科学
·
化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Wei Zhang,Guokang Han,Changpeng Liu,Xue Zhang,Wei Xing,Chunyu Du
Co-centered single-atom catalysts (SACs) have emerged as an increasingly promising non-platinum group candidate for acidic oxygen reduction reaction (ORR) due to their balanced activity and stability. However, the intrinsic ORR activity of present Co-centered SACs remains far below the commercial Pt/C. Herein, a CoN 3 O-structured SAC is successfully fabricated by a gas-phase strategy and achieves a peak power density of 492.6 mW cm −2 under the 1.0 bar H 2 /air condition, demonstrating its excellent application potential in practical fuel cells. Unique electron-feeding mechanism is revealed to account for the remarkably enhanced ORR activity inner CoN 3 O SAC. It is indicated that the electron interaction inner active site governed by both electronegativity in σ bond and d-p back-feeding in π bond reaches balance at CoN 3 O, thus optimized adsorption of oxygen-containing intermediates. Our work provides multiple insights into the orbital scale laws for higher-performance PGM-free ORR catalysts.
研究领域:
材料科学
·
催化化学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2025
·
IF 14.1
Haomiao Bai,Sujun Ding,Yanfei Dai,Jiefu Liu,Huangjing Chen,Wei Feng,Dehong Yu,Yu Chen,Xuejun Ni
Piezoelectric semiconductor nanomaterials have attracted considerable interest in piezocatalytic tumor treatment. However, piezocatalytic therapy encounters obstacles such as suboptimal piezoelectric responses, rapid electron-hole recombination, inefficient energy harvesting, and the complexities of the tumor microenvironment. In this study, sulfur vacancy-engineered cobalt (Co) single-atom doped molybdenum disulfide (SA-Co@MoS 2 ) nanoflowers are strategically designed, which exhibit enhanced piezoelectric effects. Specifically, the introduction of Co single atom not only induces lattice distortion and out-of-plane polarization but also leads to the formation of numerous sulfur vacancies. These changes collectively narrow the intrinsic bandgap of the material, facilitating effective separation and migration of charge carriers, and enabling efficient production of reactive oxygen species under ultrasound stimulation. Additionally, the SA-Co@MoS 2 nanoflowers demonstrate improved enzymatic activity and exhibit glutathione depletion capabilities attributed to the mixed valence states of Co, intensifying oxidative stress in tumor cells, and leading to cell cycle arrest and apoptosis, while the inactivation of glutathione peroxidase 4 induces ferroptosis. Both in vitro and in vivo results indicate that SA-Co@MoS 2 nanoflowers can significantly eliminate tumor cells. This study offers valuable insights into the exploration of single-atom doping-enhanced piezoelectric sonosensitizers for cancer treatment, potentially paving the way for advancements in the field of piezocatalytic synergistic enzyodynamic therapy.
研究领域:
材料科学
·
肿瘤学
·
纳米医学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yue Xin,Hongjie Wang,Hao Xue,Qiang Li,Huanxin Li,Yue Zhang,Yanzhi Dong,Haijiao Xie,Yiyang Ma
Cobalt atoms anchored on Ti 3 C 2 -based MXene (i.e., Co-SA/MXene) have been successfully endowed with exceptional catalytic performance for the elimination of aqueous micropollutants. Herein, we firstly proposed a coupling method of etching-exfoliation-reduction to enrich titanium vacancies. The as-synthesized Co-SA/MXene exhibited a superior removal efficiency of ranitidine of 100 %, and the corresponding reaction kinetics constant (μmol/s•g) was 1.11–6643.53 times higher than the state-of-the-art for ranitidine degradation. The introduction of abundant titanium vacancies enabled a long-lasting life via an accelerated valence cycling of Co(II) and Co(III), and also effectively inhibited toxic Co 2 + leaching. DFT revealed that O II /O III dual-atoms were more suitable for PMS adsorbing while offering stronger adsorption energy, and further offered a new insight into the PMS activation mechanism for 1 O 2 selected generation. This work revealed that oxidation behavior of ranitidine and established an attractive water treatment technique for the rapid removal of aqueous micropollutants.
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
危险品化学品经营许可证（带存储）