Nature Synthesis
·
2022
·Vol. 1
·期 9
·719-728
·
IF 0
Hao Qi,Zhong Hai-xia,Wang Jia-zhi,Liu Kai-hua,Yan Jun-min,Ren Zhou-hong,Zhou Na,Zhao Xiao,Zhang Hao,Liu Dong-xue,Liu Xi,Chen Li-wei,Luo Jun,Zhang Xin-bo
Dual-atom catalysts, combining single-atom catalysts and metal alloys, are promising electrocatalysts for CO 2 reduction but are limited by sluggish CO 2 reduction kinetics and ill-defined dual-atom sites. Here, we develop a catalyst of Ni dual-atom sites via in situ conversion of nanoparticles into dual atoms. We achieve efficient electrocatalytic CO 2 reduction on Ni dual-atom catalysts with a CO partial current density up to ~1 A cm −2 and turnover frequency of 77,500 h −1 at >99% Faradaic efficiency. In situ X-ray absorption and theoretical calculations reveal that during the catalytic process the Ni dual-atom sites trigger the adsorption of hydroxyl (OH ad ), forming electron-rich active centres that endow a moderate reaction kinetic barrier of *COOH formation and *CO desorption. The resultant catalytic microenvironment enables expedited kinetics compared with either the kinetics of bare dual-atom sites or OH ad regulated single-atom sites.
研究领域:
材料科学
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催化化学
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环境科学
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DOI
Nature Energy
·
2024
·
IF 49.7
Xu Zhanyou,Lu Ruihu,Lin Zih-Yi,Wu Weixing,Tsai Hsin-Jung,Lu Qian,Li Yuguang C.,Hung Sung-Fu,Song Chunshan,Yu Jimmy C.,Wang Ziyun,Wang Ying
The electrochemical CO 2 reduction reaction towards value-added fuel and feedstocks often relies on metal-based catalysts. Organic molecular catalysts, which are more acutely tunable than metal catalysts, are still unable to catalyse CO 2 to hydrocarbons under industrially relevant current densities for long-term operation, and the catalytic mechanism is still elusive. Here we report 3,5-diamino-1,2,4-triazole-based membrane electrode assemblies for CO 2 -to-CH 4 conversion with Faradaic efficiency of (52 ± 4)% and turnover frequency of 23,060 h −1 at 250 mA cm −2 . Our mechanistic studies suggest that the CO 2 reduction at the 3,5-diamino-1,2,4-triazole electrode proceeds through the intermediary *CO 2 –*COOH–*C(OH) 2 –*COH to produce CH 4 due to the spatially distributed active sites and the suitable energy level of the molecular orbitals. A pilot system operated under a total current of 10 A (current density = 123 mA cm −2 ) for 10 h is able to produce CH 4 at a rate of 23.0 mmol h −1 .
研究领域:
电化学
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催化
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可再生能源
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材料科学
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产品关联
DOI
高影响因子
ACS Nano
·
2021
·
IF 15.881
Jianbin Liu,Dashuai Wang,Kang Huang,Juncai Dong,Jiangwen Liao,Sheng Dai,Xuan Tang,Minmin Yan,Haisheng Gong,Jingjing Liu,Zhichao Gong,Rui Liu,Chunyu Cui,Gonglan Ye,Xiaolong Zou,Huilong Fei
The development of strategies for tuning the electronic structure of the metal sites in single-atom catalysts (SACs) is the key to optimizing their activity. Herein, we report that iodine doping within the carbon matrix of a cobalt–nitrogen–carbon (Co–N–C) catalyst can effectively modulate its electronic structure and catalytic activity toward the hydrogen evolution reaction (HER). The iodine-doped Co–N–C catalyst shows exceptional HER activity in acid with an overpotential of merely 52 mV at 10 mA cm–2, a small Tafel slope of 56.1 mV dec–1, making it among the best SACs based on both precious and nonprecious metals. Moreover, this catalyst possesses a high turnover frequency (TOF) value of 1.88 s–1 (η = 100 mV), which is about 1 order of magnitude larger than that (0.2 s–1) of the iodine-free counterpart. Experimental and theoretical studies demonstrate that the introduction of iodine dopants lowers the chemical oxidation state of the Co sites, resulting in the optimized hydrogen adsorption and facilitated HER kinetics. This work provides an alternative strategy to regulate the electronic structure of SACs for improved performance.
研究领域:
材料科学
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电化学
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催化
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产品关联
DOI
PubMed
高影响因子
FUEL
·
2025
·
IF 7.5
Lipeng Guo,Jihui Yao,Haibo Zhu
Methylcyclohexane (MCH) dehydrogenation for H 2 production is a promising route in liquid organic hydrogen carriers technology. However, there are few reports on the influence of Pt size on methylcyclohexane dehydrogenation under different reaction atmospheres. In this study, a series of Pt/Al 2 O 3 catalysts with Pt particle sizes ranging from 0.67 to 1.26 nm were prepared via the impregnation method. The influences of Pt particle size on MCH dehydrogenation under H 2 and N 2 atmospheres were investigated. The toluene (TOL) product adsorbed on Pt site has a significant effect on the activity and stability of Pt/Al 2 O 3 for MCH dehydrogenation. Under N 2 atmosphere, the poisoning of Pt/Al 2 O 3 by toluene leads to a low activity in this reaction. By contrast, under H 2 atmosphere, the adsorption of toluene can be effectively inhibited by H 2 , and thus an enhanced catalytic performance can be achieved. The catalyst with Pt size of 0.67 nm exhibits a high turnover frequency (TOF) of 33,530 mol H2 ·mol Pt −1 ·h −1 , corresponding to a H 2 evolution rate of 2,865 mmol·g Pt −1 ·min −1 . These findings provide a deeper understanding of the dependence of catalyst structure and reaction conditions on MCH dehydrogenation, offering fundamental guidance for the design of efficient catalysis system for MCH dehydrogenation.
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DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2020
·Vol. 36
·期 6
·1013-1016
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IF 1.063
Yu Qiuying,Lin Xiu,Li Xinhao,Chen Jiesheng
Heterogeneous catalysts have been developed for C-C coupling reactions, but stand low activity and always proceed under harsh conditions. Photocatalytic Stille cross-coupling reaction as a green catalytic method for C-C bond formation is of great interest for a wide range of scientists but still lacks stable and highly efficient catalysts. Herein, we have designed an Au nanoparticle-graphitic carbon nitride heterojunction as an outstanding photo-catalyst for artificial photosynthesis in Stille cross-coupling reaction. The interface effect between metal and semiconductor makes electron rectify and prevents the recombination of electron-hole pairs. Moreover, the efficiency of Au nanoparticle catalysts could be adjusted by gold contents. Thus the turnover frequency(TOF) value reached the highest level of 788 h −1 over the optimal heterojunction catalyst. Most importantly, the C-C bond formation reaction has been proved to be carried out well under visible light irradiation, indicating the low-cost organic synthesis process. Further analysis confirmed the stability and general application of our heterogeneous Au nano-heterojunction catalyst.
研究领域:
化学
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材料科学
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催化
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光化学
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DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Sheng Huixiang,Wang Jin,Huang Juhui,Li Zhuoyao,Ren Guozhang,Zhang Linrong,Yu Liuyingzi,Zhao Mengshuai,Li Xuehui,Li Gongqiang,Wang Ning,Shen Chen,Lu Gang
The reaction efficiency of reactants near plasmonic nanostructures can be enhanced significantly because of plasmonic effects. Herein, we propose that the catalytic activity of molecular catalysts near plasmonic nanostructures may also be enhanced dramatically. Based on this proposal, we develop a highly efficient and stable photocatalytic system for the hydrogen evolution reaction (HER) by compositing a molecular catalyst of cobalt porphyrin together with plasmonic gold nanoparticles, around which plasmonic effects of localized electromagnetic field, local heating, and enhanced hot carrier excitation exist. After optimization, the HER rate and turn-over frequency (TOF) reach 3.21 mol g −1 h −1 and 4650 h −1 , respectively. In addition, the catalytic system remains stable after 45-hour catalytic cycles, and the system is catalytically stable after being illuminated for two weeks. The enhanced reaction efficiency is attributed to the excitation of localized surface plasmon resonance, particularly plasmon-generated hot carriers. These findings may pave a new and convenient way for developing plasmon-based photocatalysts with high efficiency and stability.
研究领域:
材料科学
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纳米技术
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光催化
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化学工程
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
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2023
·
IF 7.3
Zhenping Cai,Yongxin Ding,Jiayin Zhang,Panjie Yu,Yongde Ma,Yanning Cao,Ying Zheng,Kuan Huang,Lilong Jiang
Dispersed metal sulfides are promising catalysts for the hydroconversion of biolipids to produce second-generation biodiesel. In this work, oil-soluble Mo-based ionic liquids (ILs) were innovatively utilized as the precursors for in situ generation of MoS 2 catalysts for the hydroconversion of biolipids. Taking methyl palmitate as the model compound, the excellent activity of in situ generated MoS 2 from ionic liquid Mo-based precursors was obtained. The turnover frequencies (TOFs) reached up to 1.6 × 10 2 h −1 for methyl palmitate conversion and 83 h −1 for hexadecane (C 16 ) yield at 320 °C and 0.5 h (42% conversion) under solvent-dilute conditions. The structures of in situ generated MoS 2 catalysts were characterized to provide explanations for the catalytic results. Based on the product distributions, the pathway of methyl palmitate hydroconversion was proposed, and the kinetics of methyl palmitate hydroconversion was analyzed in further detail. Applying the Mo-based ILs in the hydroconversion of methyl palmitate and palm oil under solvent-free condition also granted high conversions of feeds and selectivities of HDO products.
研究领域:
催化
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化学工程
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可再生能源
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绿色化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
·
IF 20.2
Yan Liu,Liwen Xing,Yaqi Liu,Dianxing Lian,Mohaoyang Chen,Weiwei Zhang,Ke Wu,Hongdan Zhu,Zhiyi Sun,Wenxing Chen,Peng Wu,Dingsheng Wang,Yongjun Ji
The intrinsic activity of single-atom catalysts is influenced by the local electronic structures of metal centers, with existing modulation strategies limited to adjacent atomic coordination. However, the impacts of support surface geometry on local bonding environment, and thus electronic structures of single-atom centers have rarely been known. Here, we prepared highly curved B,N co-doped carbon-supported ruthenium catalyst with an ultra-low Ru loading of 0.4 wt%, which exhibited an ultrahigh turnover frequency (TOF) of 10 H 2 s −1 (38 times that of Pt/C) and superior stability in alkaline hydrogen evolution reaction (HER). We found that curving support surface induced the strain, resulting in 1.5% compressed Ru-N and 4% stretched Ru-B bonds, leading to the accumulation of positive charge and quenching of spin polarization at Ru sites, thereby achieving the optimal binding of H* and enhanced performance for HER. This work highlights the significant support effects upon the structural design of active sites.
研究领域:
催化
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材料科学
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化学
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能源科学
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产品关联
DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2021
·Vol. 36
·期 1
·e6453
·
IF 4.105
Chun-Li Wang,Hao Yang,Juan Du,Shu-Zhong Zhan
In this work, two complexes with bipyridine ligand, [Co (bpy) 2 (SCN) 2 ] 1 and [Ni (bpy) 2 (SCN) 2 ] 2 have been prepared and well determined by single crystal X-crystallography, power X-ray diffraction (XRD), IR spectra, and so forth. Both exhibit good catalytic activity for electrochemical- and photochemical driven-hydrogen evolution. Complexes 1 and 2 can electro-catalyze H 2 evolution from a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 699.6 and 1469 mol H 2 /mol catalyst/h at an overpotential (OP) of 837.6 mV, respectively. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid as a sacrificial electron donor, complexes 1 and 2 also can photo-catalyze H 2 evolution from water. Under an optimal condition, the turnover numbers (TONs) reach 10,600 (complex 1 ) and 15,180 (complex 2 ) mol of H 2 per mol of catalyst during 48-h irradiation, respectively. The average apparent quantum yields (AQYs) of complex 1 and complex 2 are 15.07% and 22.7%, respectively. Electrochemical and photochemical investigations show that the nickel complex has a higher activity for hydrogen evolution than that of the cobalt complex. These results can provide a new insight into design and manufacture of new H 2 -production catalyst. Highlights Reactions of bipyridine (bpy), KSCN and M II Cl 2 (M = Co and Ni) afford [Co (bpy) 2 (SCN) 2 ] 1 and [Ni (bpy) 2 (SCN) 2 ] 2 , respectively. Under an overpotential (OP) of 837.6 mV, 1 and 2 provide 699.6 and 1469 mol H 2 /mol catalyst/h from buffer solution, respectively. Complexes 1 and 2 also can photo-catalyze H 2 evolution with a turnover number (TON) of 10,544 and 15,160, respectively, respectively. Complex 2 exhibits a much higher catalytic efficiency for hydrogen production than 1 . The result is attributed to that nickel exhibits higher electronegativity than cobalt, amenable to binding to H + and hydrogen production, and a smaller bandgap in [Ni (bpy) 2 (SCN) 2 ] (1.104 eV) than in [Co (bpy) 2 (SCN) 2 ] (1.7443 eV).
研究领域:
催化
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电化学
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光化学
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材料科学
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产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2023
·Vol. 35
·期 28
·2302485
·
IF 29.4
Leilei Yin,Shuai Zhang,Mingzi Sun,Siyuan Wang,Bolong Huang,Yaping Du
For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, and N co-doped hollow carbon substrate (Ce SAs/PSNC) for the oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses a half-wave potential of 0.90 V, a turnover frequency value of 52.2 s −1 at 0.85 V, and excellent stability for the ORR, which exceeds the commercial Pt/C and most recent SACs. Ce SAs/PSNC-based liquid zinc–air batteries (ZABs) exhibit a high and stable open-circuit voltage of 1.49 V and a maximum power density of 212 mW cm −2 . As the catalyst of the air cathode, it also displays remarkable performance in flexible electronic devices. Theoretical calculations reveal that the introduction of S and P sites induces significant electronic modulations to the Ce SA active sites. The P and S dopings promote the electroactivity of Ce SAs and improve the overall site-to-site electron transfer within the Ce SAs/PSNC. This work offers a unique perspective for modulating RE-based SACs in a complex coordination environment toward superior electrocatalysis and broad applications in energy conversion and storage devices.
研究领域:
材料科学
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电化学
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能源存储与转化
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催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2023
·
IF 7.3
Suting Xie,Xinyu Zhao,Jiabao Bai,Zhihua Yang,Hou Chen,Lixia Yang,Ying Liang,Liangjiu Bai,Huawei Yang
Aerobic oxidative desulfurization (AODS) offers a sustainable and cost-effective alternative to conventional diesel desulfurization techniques. However, despite its potential, the development of catalysts with both high activity and stability remains a critical challenge in this field. Here we present the synthesis of polyoxometalate (POM) derived Co,N-codoped MoO x nanoclusters on graphene sheets for boosting the AODS reactions, which combines the characteristics of sub-nanometer size of POMs and excellent stability of metal oxides. Through experimental characterizations and density functional theory (DFT) calculations, we demonstrate that the MoO x nanoclusters can effectively activate O 2 by electron transfer, while the doped Co and N elements further optimize the electronic structure of Mo sites, resulting in a significant enhancement in catalytic activity. The optimized catalyst exhibits an impressive turnover frequency of 67.88 h −1 in the oxidation of dibenzothiophene (DBT), facilitating the rapid conversion of various thiophenes under mild conditions. The catalyst also demonstrates prominent durability in seven cycles of reuse with consistent catalytic performance and unchanged chemical structure. More importantly, the catalyst achieves deep AODS of real diesel, showcasing its potential for practical applications.
研究领域:
催化
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材料科学
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环境化学
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能源
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产品关联
DOI
高影响因子
Nature Communications
·
2020
·Vol. 11
·期 1
·1-11
·
IF 12.121
Zhang Ning,Feng Xiaobin,Rao Dewei,Deng Xi,Cai Lejuan,Qiu Bocheng,Long Ran,Xiong Yujie,Lu Yang,Chai Yang
Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni 4+ species in surface reconstructed (oxy)hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni 4+ species, which is energetically favored by the multistep evolution of Ni 2+ →Ni 3+ →Ni 4+ . The dynamically constructed Ni 4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A g metal −1 and 0.483 s −1 at an overpotential of 300 mV in alkaline electrolyte, respectively.
研究领域:
电化学
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催化
·
材料科学
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表面科学
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DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）