JOURNAL OF CATALYSIS
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2022
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IF 8.047
Xiaodong Zhang,Fukun Bi,Zhenyuan Zhao,Yang Yang,Yintao Li,Liang Song,Ning Liu,Jingcheng Xu,Lifeng Cui
Supported single-atoms and sub-nanometre clusters have exhibited superb catalytic performance toward many reactions. However, inactivation of single-atom or cluster catalysts in complex reactive conditions poses major challenge for their practical application. Herein, we demonstrate that the prepared Pd-UiO-66 with ultra-low Pd loading (0.05 wt%) contains three robust active Pd species, (isolated Pd atom (Pd 1 ), sub-nanometre Pd clusters (Pd c ) and Pd nanoparticles (Pd n )) and presents superb activity for toluene oxidation and water resistance (10.0 vol%). Experiments and theoretical calculations firstly confirm that consecutive H 2 -O 2 and reaction gas treatment (1000 ppm toluene in 20 vol.%O 2 /Ar) induce residual N species from solvent N, N-dimethylformamide to enter UiO-66 skeleton forming Pd 1 -N 1 structures. DFT calculations reveal that the synergistic effect of Pd species (namely, the enhanced activation of O 2 and H 2 O by Pd 1 and the improved adsorption of toluene by Pd c and Pd n ) is the main factor for the excellent activity of Pd-U-H-O-reused catalyst.
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Sustainability
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2023
·Vol. 6
·期 7
·816-826
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IF 27.6
Lei Xin,Tang Qingyun,Zheng Yongping,Kidkhunthod Pinit,Zhou Xiaolong,Ji Bifa,Tang Yongbing
The electrocatalytic oxygen reduction and evolution of molecular oxygen, known as oxygen electrocatalysis, is one of the most important reactions that are central to a range of energy and environmental technologies. While the current best-performing electrocatalysts remain dominated by precious metals, carbon-based systems provide a compelling alternative owing to their intrinsic sustainability and practical applicability. Here we show a design guided by theoretical calculations that pushes the activity boundaries of carbon electrocatalysts to an unprecedented level. The rationale is that incorporating high-entropy heteroatoms could effectively minimize the local symmetry to destabilize the π-electron network of graphitic carbons and avoid too strong or too weak binding energies for intermediate species of the oxygen reduction reaction and the oxygen evolution reaction. Accordingly, our catalyst embeds five metal single atoms—Fe, Mn, Co, Ni and Cu—and two sources of N, and it exhibits superior bifunctional activities in an alkaline environment that exceed the oxygen reduction reaction and evolution reaction performance of commercial Pt/C and RuO 2 catalysts, respectively. Our work establishes electrocatalyst design principles that could open the door to sustainable solutions for critical green technologies such as fuel cells, batteries and water splitting.
研究领域:
能源材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Pharmaceutics
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2023
·Vol. 15
·期 4
·1217
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IF 5.4
Tushuai Li,Yue Gu,Lisha Yu,Shenglong Zhu,Jie Zhang,Yongquan Chen
Tumor microenvironment (TME)-induced nanocatalytic therapy is a trending strategy for tumor-targeting therapy, but the low catalytic efficiency remains to limit its therapeutic effect. The single-atom catalysts (SACs) appear as a novel type of nanozymes that possesses incredible catalytic activity. Here, we developed PEGylated manganese/iron-based SACs (Mn/Fe PSACs) by coordinating single-atom Mn/Fe to nitrogen atoms in hollow zeolitic imidazolate frameworks (ZIFs). Mn/Fe PSACs catalyze cellular hydrogen peroxide (H2O2) converting to hydroxyl radical (•OH) through a Fenton-like reaction; it also enhances the decomposition of H2O2to O2that continuously converts to cytotoxic superoxide ion (•O2−) via oxidase-like activity. Mn/Fe PSACs can reduce the depletion of reactive oxygen species (ROS) by consuming glutathione (GSH). Here, we demonstrated the Mn/Fe PSACs-mediated synergistic antitumor efficacy among in vitro and in vivo experiments. This study proposes new promising single-atom nanozymes with highly efficient biocatalytic sites and synergistic therapeutic effects, which will give birth to abundant inspirations in ROS-related biological applications in broad biomedical fields.Keywords:tumor microenvironment;single-atom catalysts;reactive oxygen species;synergistic antitumor
研究领域:
纳米技术
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癌症生物学
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生物医学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Science China-Materials
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2023
·Vol. 66
·期 6
·2475-2482
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IF 8.1
Cai Chunqi,Chen Qingqing,Su Hongyan,Huang Pengcheng,Mao Junjie,Wu Fang-Ying
The detoxification of nerve agents, a class of extremely toxic chemical warfare agents, is urgently needed because they have remained a threat to humanity. To date, zirconium-based metal-organic frameworks (Zr-MOFs) are the most popular catalysts in this realm. However, it is still essential to develop new and efficient catalysts based on Zr-MOFs to achieve more rapid hydrolysis. Herein, we report that the single-atom catalyst (SAC) with Cu single atoms on a UiO-66-NH 2 support (Cu@UiO-66-NH 2 ) could significantly boost the degradation of the nerve agent simulant. Compared with the pristine UiO-66-NH 2 , this SAC exhibited remarkable catalytic activity with a half-life for hydrolysis of ∼2 min and better reusability in cyclic experiments. Both experimental and theoretical studies suggest that the atomically dispersed Cu species anchored to the amino groups rather than to the Zr 6 node of UiO-66-NH 2 acted as the catalytic active sites, leading to favorable binding geometries with the substrate and the product. A catalytic mechanism on the SAC different from that generally considered on the pristine Zr-MOFs was thus presented to elucidate the enhanced catalytic efficiency.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Kaiyang Xu,Yu Chen,Hua Yang,Yuyan Gan,Lizhi Wu,Li Tan,Yihu Dai,Yu Tang
Cyclohexanone is an important raw material for manufacturing nylon and other chemicals. The sustainable conversion of biomass derived molecules to cyclohexanone is desired but still challenging. Herein, a palladium single atom catalyst anchored in the micropores of zeolite (namely Pd 1 /ZSM-5) is designed and exhibits remarkable catalytic activity in transforming anisole to cyclohexanone in water medium (H 2 O), without using of organic solvent or halogen promoter. The selectivity to cyclohexanone is 91.2% and the turnover rate (TOR) is 400.8 h −1 at 453 K. The Pd sites, acid sites, and microporous confinement environment of zeolite cooperate to promote the partial hydrogenation to cyclohexanone, and inhibit further hydrogenation as the side reaction. H 2 O not only acts as the solvent, but also participates significantly in the partial hydrogenation. Moreover, as revealed by isotope labelled experiments (D 2 O and H 2 18 O), the water participated hydrogenolysis and the consequent partial hydrogenation mechanism is proposed.
研究领域:
催化化学
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绿色化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2021
·Vol. 9
·期 2
·302-309
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IF 6.569
Jiayu Xin,Fei Li,Zhen Li,Jiaqi Zhao,Yu Wang
Single-atom dispersed carbon nitride photocatalysts have been extensively associated with clean energy conversion, storage and utilization. However, it is still a challenge to elucidate the relationship between the electronic structure of catalysts and their photocatalytic properties. In this work, single atom Ag/C3N4 catalysts have been prepared via pyrolyzing cyanuric acid, AgNO3 and melamine as precursors. We observe that their photocatalytic activity increases on increasing the concentration of Ag from 0.32% to 0.53%, and subsequently decreases on further increasing the concentration of Ag, which indicates that the concentration of Ag atoms can control the performance of single-atom catalysts. Deep investigations suggest that the concentration of Ag atoms can modulate the bottom of the conduction band (CB) and the maximum of the valence band (VB). The higher the bottom of the CB is, the better the performance of catalysts is. In contrast to bulk carbon nitride, the rate constants of the optimized single-atom photocatalyst Ag/C3N4 with 0.53% Ag for rhodamine B (RhB) and tetracycline (TC) degradation are enhanced approximately 165.3 and 24.9 times, respectively. Furthermore, the ESR spectrum shows that the superoxide radical plays a major role in the photocatalytic process. This work provides a new insight into the structure–property relationship and our strategy provides guidance for the synthesis of other single-atom photocatalysts.
研究领域:
材料科学
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环境科学
✓ 已验证
DOI
高影响因子
CARBON
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2022
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IF 11.307
Xilong Wang,Hongwei Zhu,Chen Yang,Jiajia Lu,Lirong Zheng,Han-Pu Liang
Single-atom Fe–N–C electrocatalysts are attracting more attentions as one most promising transition metal based single-atom catalyst towards the oxygen reduction reaction (ORR). However, the inaccessibility of internal Fe-N x active sites and insufficient stability hinder their large-scale application. Herein, a facile benzoate-assisted self-template strategy which could dramatically enhance the oxygen reduction reaction catalytic performance and stability of ZIF-8 derived atomically dispersed Fe–N–C catalysts (Fe-SA/Meso-C) is developed. The sodium benzoate used in the present work is effective for promoting the formation of Fe–N–C catalysts with denser accessible active sites as well as mesopores with diameters ranging from 2.5 to 5 nm. These structural advantages make the synthesized Fe-SA/Meso-C catalysts afford excellent electrocatalytic performance for the ORR in 0.1 M KOH with a positive half-wave potential (E 1/2 ) of 0.926 V vs. RHE and exceptionally high kinetic current density (J k ) of 92.5 mA cm −2 at 0.85 V. Beyond that, Fe-SA/Meso-C shows outstanding long-term stability with over 90% activity retain after 90 h chronoamperometry i-t test as well as superior tolerance to methanol crossover . More importantly, the assembled zinc-air battery with Fe-SA/Meso-C as the cathode material achieves a high peak power density of 166.2 mW cm −2 and a high specific capacity of 776.1 mA h g −1 . Our results reveal that small mesopores in atomically dispersed Fe–N–C electrocatalysts could facilitate mass transport, increase the accessibility of active sites and optimize the interface between electrolyte and carbon matrix, thus optimizing their electrocatalytic performance for the ORR. This work paves a way to the design and synthesis of stable single-atom electrocatalysts with optimized structure, electrochemical performance and promising applications.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
Industrial Chemistry & Materials
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2022
·Vol. 1
·期 1
·106-116
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IF 0
Wen Yao,Chenghong Hu,Yajie Zhang,Hao Li,Fengliang Wang,Kui Shen,Liyu Chen,Yingwei Li
Nitrogen-rich zeolitic imidazolate frameworks (ZIFs) are ideal precursors for the synthesis of metal single atoms anchored on N-doped carbon. However, the microporous structures of conventional ZIFs lead to low mass transfer efficiency and low metal utilization of their derivatives. Here, we construct a composite of Co single atoms anchored on nitrogen-doped carbon with a three-dimensional ordered macroporous structure (Co-SA/3DOM-NC) by two-step pyrolysis of ordered macro/microporous ZnCo-ZIF. Co-SA/3DOM-NC shows high activity in the oxidative esterification of furfural, achieving a 99% yield of methyl 2-furoate under mild reaction conditions, which is significantly superior to the microporous and the Co-nanoparticle counterparts. The high activity of Co-SA/3DOM-NC should be attributed to the CoN4 centers with high intrinsic activity and the ordered macroporous structure, promoting the mass transfer of reactants and accessibility of active sites.
Keywords: Heterogeneous catalysis; Hierarchical pores; Ordered macropore; Oxidative esterification reaction; Single-atom catalysts.
研究领域:
化学工程
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材料科学
✓ 已验证
DOI
ACS Nano
·
2021
·
IF 15.881
Peilong Lu,Xin Tan,Haitao Zhao,Qian Xiang,Kaili Liu,Xiaoxu Zhao,Xinmao Yin,Xinzhe Li,Xiao Hai,Shibo Xi,Andrew T S Wee,Stephen J. Pennycook,Xuefeng Yu,Menglei Yuan,Jianbo Wu,Guangjin Zhang,Sean C. Smith,Zongyou Yin
An atomically dispersed structure is attractive for electrochemically converting carbon dioxide (CO2) to fuels and feedstock due to its unique properties and activity. Most single-atom electrocatalysts are reported to reduce CO2 to carbon monoxide (CO). Herein, we develop atomically dispersed indium (In) on a nitrogen-doped carbon skeleton (In–N–C) as an efficient catalyst to produce formic acid/formate in aqueous media, reaching a turnover frequency as high as 26771 h–1 at −0.99 V relative to a reversible hydrogen electrode (RHE). Electrochemical measurements show that trace amounts of In loaded on the carbon matrix significantly improve the electrocatalytic behavior for the CO2 reduction reaction, outperforming conventional metallic In catalysts. Further experiments and density functional theory (DFT) calculations reveal that the formation of intermediate *OCHO on isolated In sites plays a pivotal role in the efficiency of the CO2-to-formate process, which has a lower energy barrier than that on metallic In.
研究领域:
化学
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材料科学
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催化反应
✓ 已验证
DOI
高影响因子
Energy & Environmental Materials
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2024
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IF 13
Shuai Cao,Wenzhuo Wu,Chaozhong Liu,Leqian Song,Qun Xu,Huacheng Zhang,Yanli Zhao
The development of active water oxidation catalysts for water splitting has stimulated considerable interest. Herein, the design and building of single atom Co sites using a supramolecular tailoring strategy are reported, that is, the introduction of pillar[4]arene[1]quinone (P4A1Q) permits mononuclear Co species stereoelectronically assembled on MoS 2 matrix to construct an atomically dispersed MoS 2 @Co catalyst with modulated local electronic structure, definite chemical environment and enhanced oxygen evolution reaction performance. Theoretical calculations indicate that immsobilized single-Co sites exhibit an optimized adsorption capability of oxygen-containing intermediates, endowing the catalyst an excellent electrocatalytic oxygen evolution reaction activity, with a low overpotential of 370 mV at 10 mA cm −2 and a small Tafel slope of 90 mV dec −1 . The extendable potential of this strategy to other electrocatalysts such as MoS 2 @Ni and MoS 2 @Zn, and other applications such as the hydrogen evolution reaction was also demonstrated. This study affords new insights into the rational design of single metal atom systems with enhanced electrocatalytic performance.
研究领域:
材料科学
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电催化
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能源化学
✓ 已验证
DOI
高影响因子
Chem Catalysis
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2024
·
IF 11.5
Fei-Yang Yu,Hao Sun,Hua-Qiao Tan,Yang-Guang Li,Shuit-Tong Lee,Zhen-Hui Kang
The dynamic evolution and structure-performance relationships of single-atom catalysts (SACs) under operating conditions are one of the most concerned hotspots at present. Here, we employed Anderson-type polyoxometalates as a precursor to prepare the SAC Rh-MoS 2 , which shows excellent hydrogen evolution reaction (HER) performance with a mass activity of 4.26 A mg −1 at 100 mV. Such a result is much better than that of 20% Pt/C. Extensive experimental characterization combined with density functional theory (DFT) calculations suggest that the active site undergoes a dynamic evolution from Rh-S to Rh-S/O, while at the same time, the support is transformed from 1T MoS 2 to 1T-2H MoS 2 . It is this dynamic evolution of the catalyst structure that causes a series of changes in the activity, and eventually, a balance between catalytic activity and stability is achieved. This work offers a good research demonstration of the dynamic evolution of SACs under operating conditions and provides a new perspective on the design of SACs.
研究领域:
材料科学
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理论化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2024
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IF 5.8
Fenghui Li,Xuhui Li,Yawei Jiang,Yingjie Cao,Wenjian Fang,Tao Zhou,Jiang Wu,Yongsheng Liu
Photocatalysis has gained significant attention in recent years for water splitting, with graphitic carbon nitride (g-C 3 N 4 ) emerging as a promising candidate. However, the low carrier mobility and the lack of active sites for hydrogen evolution limit photocatalytic hydrogen evolution performance. Herein, this work presents a facile approach to achieve single Mo sites with a unique local coordination structure featuring one Mo atom coordinated with two nitrogen atoms and one sulfur atom . Among the prepared photocatalysts , 6 wt % Mo/SCN exhibits the highest photocatalytic hydrogen evolution activity with a yield rate of 4.05 mmol g -1 h -1 , which is 13 times higher than that of pure g-C 3 N 4 and superior to most of the g-C 3 N 4 series photocatalysts. Experimental results and density functional theory calculations confirm that the Mo single-atom and S atom have synergistic catalysis under the co-modification, and the formed Mo-S bonds will enhance the ability of the substrate to anchor the Mo single-atom to enhance the stability of the photocatalyst. This work offers insights into transition metal single-atom and synergistic catalysis design for photocatalytic hydrogen evolution.
研究领域:
材料科学
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能源化学
✓ 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）