ACS Catalysis
·
2024
·
IF 11.3
Longjian Li,Junhui Wang,Qinhua Zhang,Shuai Wang,Hangkai Zhang,Tao Xing,Mingqing Wang,Mingbo Wu,Zhenxing Wang,Wenting Wu
Near-infrared light occupies 54.3% of the solar spectrum and has greater penetration depth, and its effective utilization is of great significance in the practical application of photocatalysis on a larger scale. However, the development of catalysts that can directly utilize near-infrared light is still a huge challenge. This paper proposes a strategy to directly utilize near-infrared light (excitation wavelength extending to 850 nm) by creating carbon material doped with a high-spin-state Co(II)-Nx single-atom site. In the near-infrared-light-irradiated photooxidation of 1,5-dihydroxynaphthalene, the yield of juglone can reach 45% without a significant decrease, even when the catalytic volume is increased by 20 times, which was much higher than that irradiated by 460 nm wavelength (reduced by about 23%). Our study sets the stage for fabricating stable NIR photocatalysts and provides a solution to directly enhance NIR photooxidation in a large-scale manner.
研究领域:
材料科学
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光化学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
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.
研究领域:
环境科学
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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
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 23
·13678-13687
·
IF 12.732
Dan Wang,Hao Xu,Peixia Yang,Xiangyu Lu,Jingyuan Ma,Ruopeng Li,Lihui Xiao,Jinqiu Zhang,Maozhong An
Compared to individual metal sites, e.g. Fe–N4 sites, the synergistic effect of dual-metal sites can further adjust the interaction of reactants or intermediates with active sites, which is beneficial for boosting the oxygen reduction reaction (ORR) in Zn–air batteries. However, developing a simple and direct method instead of complicated procedures and post-treatment to realize well-defined dual-metal sites is still a grand challenge. Herein, a facile one-step impregnation-pyrolysis route without any post-treatment is developed to controllably synthesize Fe and Co dual-metal sites embedded in hierarchical N-doped carbon from metal–organic frameworks. X-ray absorption spectra coupled with density functional theory calculations demonstrate that the Fe–N4 and Co–N4 dual sites can synergistically enhance the ORR activity. Impressively, the well-controlled FeCo–N–C catalyst exhibits excellent ORR performance, with half-wave potentials (E1/2) of 0.807 and 0.904 V in 0.1 M HClO4 and 0.1 M KOH, respectively. Benefiting from the highly active dual-metal sites and desired porous structure, FeCo–N–C serving as a cathode catalyst achieves an uplifting peak power density of 196.3 mW cm−2 and a remarkable specific capacity of 728.6 mA h gZn−1 at a discharge current density of 20 mA cm−2 in a practical liquid Zn–air battery. Besides this, such superb battery performance is demonstrated in an all-solid-state Zn–air battery.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 9
·4807-4815
·
IF 11.301
Ying Gu,Aiping Wu,Lei Wang,Dongxu Wang,Haijing Yan,Peng Yu,Ying Xie,Chungui Tian,Fanfei Sun,Honggang Fu
Single-atom catalysts (SACs) have been promising in various catalytic fields, but the controllable synthesis of SACs with high stability remains challenging. Here, we show a robust strategy toward the fabrication of highly efficient and stable SACs based on the “competitive occupancy” of two metal (M) species on graphene oxide (GO). The abundant M1 (Ti) species predominantly occupy more groups of GO, thereby leaving a tiny number of groups in the gaps of the M1 species to combine with M2 (Co2+, etc.) species. Consequently, this guarantees the formation of Co–N4 SACs embedded in 2D TiN/rGO sheets during nitridation. Further, TiN can act as a “spacer” to prevent Co–N4 from aggregation, thereby improving catalyst stability. Co–N4/TiN–rGO exhibits outstanding catalytic performance for the fast conversion of highly concentrated aromatic nitro compounds (∼0.3–2 mM) into amino compounds and excellent recyclability, which is the best among reported catalysts. In contrast, TiN/rGO has no obvious activity, and Co4N–rGO prepared without Ti competition shows poor activity and stability, which indicates the vital role of Co–N4 and TiN for obtaining the remarkable catalytic ability of Co–N4/TiN–rGO. The reaction mechanism is also proposed based on theoretical calculations. The strategy can be used to design Ni (Fe, Cr, Cu)-based SACs.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Xiao Ge,Xinya Liu,Jinze Xu,Xiyang Zheng,Li-jiao Tian,Xiaozhi Wang
Rational regulation of the coordination environment of single-atom catalysts (SACs) is a promising yet challenging strategy to enhance their activity. Here, we introduce an O atom into the second coordination shell of Co–N4 sites via a simple thermal treatment, forming a Co–N4–ON matrix to boost photosynthetic hydrogen peroxide (H2O2) production. This modification significantly alters the electronic structure of the Co site, bringing the d-band center closer to the Fermi energy and elevating the conduction band of Co–N4–CN to enhance its reducing capacity. Density functional theory (DFT) calculations reveal intensified charge redistribution and a reduced work function in Co–N4–ON, facilitating O2 adsorption. Notably, Co–N4–ON exhibits the lowest O2 adsorption energy, indicating a stronger interaction between Co–N4–O and O2, which is further strengthened by orbital hybridization and charge transfer at their interface, leading to enhanced O2 activation. The optimized Co–N4–ON catalyst demonstrates superior O2 reduction capabilities with the lowest energy barrier during H2O2 desorption. Consequently, it achieves a H2O2 production rate of 3098.18 μmol g–1 h–1 under neutral conditions, which is 2.6 times higher than that of Co–N4–CN. Moreover, it maintains a production rate of 1967.79 μmol g–1 h–1 over 10 h in a continuous flow reactor under natural sunlight and ambient air, highlighting its durability and practicality. This study underscores the crucial role of the second coordination shell in SACs and offers valuable insights into their atomic-level structure–activity relationships, thus contributing to advancements in catalyst design for efficient photosynthetic H2O2 production.
研究领域:
化学
·
材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Meiling Fan,Peipei Liu,Yapeng Cheng,Haolin Tang,Bing Jin,Haining Zhang
Design and synthesis of earth-abundant elements-based electrocatalysts with sufficient activity and stability remain challenging for oxygen-involved electrochemical energy conversion and storage devices. In this work, catalyst with simultaneously engineered Fe-N 4 and Co-N 4 active sites and graphitic carbon multilayer-encapsulated FeCo alloy is developed by pyrolysis of metal salts doped G-g-C 3 N 4 . The obtained composite material exhibits promising catalytic activity and good stability for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte , as evidenced by the positive shift of half-wave potential by 44 mV compared to 20% Pt/C for ORR and the potential of 1.596 V at current density of 10 mAcm −2 for OER. In addition, the thus-assembled rechargeable zinc-air battery using the synthesized material as cathode delivers a maximum power density of 311.2 mWcm −2 with an open circuit potential of 1.51 V and a long-term cycling stability. DFT calculation results indicate that catalyst with composite active sites displays smaller energy barrier than that with single active site.
研究领域:
材料科学
·
电化学能源
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Dan Xu,Ruirui Liu,Jianfeng Li,Huacheng Zhao,Jiantai Ma,Zhengping Dong
Transfer hydrogenation reactions using non-noble metal-based nanocatalysts are extensively attractive due to their low-cost and green reaction conditions. But construction of such catalysts with maximum metal atom efficiency and high catalytic activity is still a challenging research goal. Here, atomically dispersed Co catalysts with Co-N 4 active sites were fabricated, which builds a bridge for transfer hydrogenation between nitroarenes and saturated N-heterocycles in aqueous solution. The TOF value of the transfer hydrogenation reaction is much higher than nanoparticle catalyst for this reaction. Density functional theory (DFT) calculations and control experiments reveal that the excellent performance origins from the Co-N 4 sites, which combines the dehydrogenation of 1,2,3,4-tetrahydroquinoline with hydrogenation of nitrobenzene in one-pot. This work not only has an in-depth understanding of active sites but also shows a unique activity to the challenging, highly efficient, and green transfer hydrogenation reaction.
研究领域:
催化化学
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材料科学
·
理论化学
✓ 已验证
DOI
高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Shizhu Song,Tian Qin,Qi Li,Yanqing Wang,Yanfeng Tang,Lifang Zhang,Xiaojuan Liu
Facile synthesis of cost-effective carbon-supported Co single atoms (Co-SAs) exhibits huge potential applications in energy storage and conversion devices. We here report the implantation of Co-SAs into hollow carbon spheres (Co-SAs-HCS) via a facile wet-chemistry strategy followed by controlled pyrolysis. Electron-rich histidine acted as a Lewis base effectively immobilizing Co2+ (Lewis acid) via the electrostatic effect and hydrogen bonds, thus achieving the scalable synthesis of Co-SAs-HCS. We constructed a series of histidine-Co2+ structure models to elucidate the formation of histidine-Co2+ complexes by analyzing their binding energy. X-ray absorption fine-structure results verify that central Co atoms with four N coordination atoms possess a non-planar Co-N4 structure. Electrochemical results indicate that the as-prepared Co-SAs-HCS catalyst shows a low potential difference (0.809 V) between the oxygen evolution reaction potential at 10 mA cm–2 and the oxygen reduction reaction half-wave potential, outperforming the commercial Pt/C catalysts (0.996 V). Moreover, an assembled Zn-air battery based on Co-SAs-HCS exhibits an unexpected long-term durability. We have demonstrated that non-planar Co-N4-1-O2 sites are the source for highly efficient adsorption and dissociation of O2 molecules and then reduction of the free energy of desorption of the intermediates by density functional theory. Our findings provide a new design insight into the exploration of advanced electrocatalysts, which will be applied in the design of green energy devices in the future.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 17
·9435-9444
·
IF 14.511
Qingshan Zhao,Wanxin Ni,Xiaojie Tan,Fengliang Cao,Tengfei Liu,Hao Huang,Zhinian Cheng,Yiwen Li,Shuwei He,Hui Ning,Mingbo Wu
Selective hydrogenation of nitroarenes to corresponding anilines is one of the most important processes in the chemical industry, which still suffers from lack of efficient catalysts with both high activity and selectivity. Herein, a reinforced single-atom Co catalyst (Co–N–CNS–Th) was rationally fabricated through a novel “Trojan horse” strategy for boosting selective hydrogenation of nitroarenes. The cobalt salt precursor is confined in a mixed molten salt (KCl + CaCl2) via recrystallization and gradually released when reaching the melting point, which can efficiently achieve atomic Co–N4 moieties accommodated in micropore defect-rich carbon nanosheets. The prepared Co–N–CNS–Th catalyst showed superior hydrogenation activity and selectivity (yield of >99%; overall TOF of 169.8 h−1) towards a series of functionalized nitroarenes under mild reaction conditions, as well as remarkable stability and reusability, standing out among the reported cobalt-based catalysts. The experimental results and DFT calculations reveal that the robust atomically dispersed Co–N4 active sites located near the edge of micropore defects can significantly accelerate the adsorption and activation of hydrogen and nitro groups, accounting for the prominent catalytic performance. This work opens a feasible avenue for the development of advanced single-atom catalysts towards selective hydrogenation of nitroarenes and beyond.
研究领域:
催化化学
·
材料科学
·
理论计算化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Guojun Li,Zheng Lian,Qiuqiu Lyu,Chenyu Zhu,Zhinian Liu,Shule Zhang,Qin Zhong
The efficiency of photocatalytic Nitric Oxide(NO) oxidation is limited by the lack of oxygen(O 2 ) active sites and poor charge carrier separation. To address this challenge, we developed a molecular Cobalt Phthalocyanine modified MIL-68(In)–NH 2 photocatalyst with a robust Built-in electric field(BIEF). In the 2 % CoPc-MIN sample, the BIEF strength is increased by 3.54 times and 5.83 times compared to pristine CoPc and MIL-68(In)–NH 2 , respectively. This BIEF facilitates the efficient S-scheme charge transfer, thereby enhancing photogenerated carrier separation. Additionally, the Co-N4(II) sites in CoPc can effectively trap the separated photoexcited electrons in the S-scheme system. In addition, the Co-N4(II) sites can also serve as active sites for O 2 adsorption and activation, promoting the generation of superoxide radical ( O 2 – ), thereby driving the direct conversion of NO to nitrate(NO 3 – ). Consequently, the 2 % CoPc-MIN sample exhibits a remarkable photocatalytic NO removal efficiency of 79.37 % while effectively suppressing the formation of harmful by-product nitrogen dioxide(NO 2 ) to below 3.5 ppb. This study provides a feasible strategy for designing high-efficiency O 2 activation photocatalysts for NO oxidation.
研究领域:
环境科学
·
材料科学
·
光催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Cheng Gao,Longzhu Li,Xiaoming Yan,Ning Zhang,Junjiang Bao,Xiaopeng Zhang,Yanqiang Li
Transition metal single atom catalysts (TM SACs) are the most promising oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) and metal-air batteries. However, the low density of M-N x active sites seriously hinders further improvement of the ORR electrocatalytic activity. Here, a strategy for encapsulating nitrogen-rich guest molecules (triethylenediamine cobalt complex, [Co(en) 3 ] 3+ ) was proposed to construct a high-performance cobalt single-atom catalyst (Co-encapsulated SAC/NC). With this strategy, the guest molecules are encapsulated into metal–organic framework (MOF) cages as an additional cobalt source to boost cobalt loading, while abundant nitrogen from guest molecules contributes to the formation of Co-N 4 active sites. Remarkably, the resulting Co-encapsulated SAC/NC has a high cobalt loading amount of 4.03 wt%, and spherical aberration-corrected transmission electron microscopy (AC-TEM) has confirmed that most cobalt exists in a single-atom state. As a result, the Co-encapsulated SAC/NC exhibits excellent ORR catalytic performance with a half-wave potential of 0.88 V. Furthermore, Zn-air batteries employing Co-encapsulated SAC/NC as air cathode show high peak power density and excellent cycling stability. Density functional theory (DFT) calculations reveal that adjacent active sites have different rate-determining steps and lower reaction energy barriers than a single active site.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2023
·Vol. 19
·期 33
·2301391
·
IF 13.3
Wenjing Zhang,Jian Zheng,Ruoyu Wang,Li Huang,Junkai Wang,Tianran Zhang,Xiangfeng Liu
Lithium–oxygen (Li–O 2 ) batteries have received extensive attention owing to ultrahigh theoretical energy density. Compared to typical discharge product Li 2 O 2 , LiOH has attracted much attention for its better chemical and electrochemical stability. Large-scale applications of Li–O 2 batteries with LiOH chemistry are hampered by the serious internal shuttling of the water additives with the desired 4e − electrochemical reactions. Here, a metal organic framework-derived “water-trapping” single-atom-Co-N 4 /graphene catalyst (Co-SA-rGO) is provided that successfully mitigates the water shuttling and enables the direct 4e − catalytic reaction of LiOH in the aprotic Li–O 2 battery. The Co-N 4 center is more active toward proton-coupled electron transfer, benefiting - direction 4e − formation of LiOH. 3D interlinked networks also provide large surface area and mesoporous structures to trap ≈12 wt% H 2 O molecules and offer rapid tunnels for O 2 diffusion and Li + transportation. With these unique features, the Co-SA-rGO based Li–O 2 battery delivers a high discharge platform of 2.83 V and a large discharge capacity of 12 760.8 mAh g −1 . Also, the battery can withstand corrosion in the air and maintain a stable discharge platform for 220 cycles. This work points out the direction of enhanced electron/proton transfer for the single-atom catalyst design in Li–O 2 batteries.
研究领域:
材料科学
·
电化学
·
能源存储
·
电池技术
✓ 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）