CHEMICAL ENGINEERING JOURNAL
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2020
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IF 10.652
Fang Wang,Ting Feng,Xiujuan Jin,Yulin Zhou,Yanjie Xu,Yahui Gao,Haisheng Li,Jianfei Lei
Herein, a robust MOFs-derived super-carbon embedding with single atom Co/Ni anode materials for LIBs is developed by one-step annealing of the core–shell precursor ZIF-8@ZIF-67 with the introduction of dimethylglyoxime nickel as Ni source. The characterization results clearly indicate that atomic Co/Ni active sites accompanied with suitable CoNi nanoparticles are evenly embedded in the MOF-derived hollow rich-nitrogen carbon matrix. Simultaneously, moderate short carbon nanotubes root in polyhedral surface under the catalytic effect from the CoNi nanoparticles and construct an advanced conductive network. As a result, it delivers a high reversible lithium-ion storage capacity of 462.1 mAh g −1 at a current density of 0.5 A g −1 over 500 cycles, excellent rate performance of 223.28 mAh g −1 even at a high current density of 2 A g −1 , which is much higher than most of reported carbon-based electrode materials. The enhanced lithium storage performance mainly derives from the moderate affinity of the Li by the atomic Co/Ni active sites incorporated with their powerful catalytic effect assisting MOF-derived rich-N doped carbon base. Moreover, the superior nano-structure of the hollow rich-nitrogen carbon skeleton with in-situ grown short carbon nanotubes improves the conductivity of electrode materials, relieves the volume expansion and accelerates the migration rate of lithium ions and electrons. The theoretical calculation further confirms the superior affinity of the Li on atomic Co/Ni active sties.
研究领域:
材料科学
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能源存储
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DOI
高影响因子
Nature Communications
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2023
·Vol. 14
·期 1
·1-12
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IF 16.6
Zhou Min,Wang Zhiqing,Mei Aohan,Yang Zifan,Chen Wen,Ou Siyong,Wang Shengyao,Chen Keqiang,Reiss Peter,Qi Kun,Ma Jingyuan,Liu Yueli
The precise construction of photocatalysts with diatomic sites that simultaneously foster light absorption and catalytic activity is a formidable challenge, as both processes follow distinct pathways. Herein, an electrostatically driven self-assembly approach is used, where phenanthroline is used to synthesize bifunctional LaNi sites within covalent organic framework. The La and Ni site acts as optically and catalytically active center for photocarriers generation and highly selective CO 2 -to-CO reduction, respectively. Theory calculations and in-situ characterization reveal the directional charge transfer between La-Ni double-atomic sites, leading to decreased reaction energy barriers of *COOH intermediate and enhanced CO 2 -to-CO conversion. As a result, without any additional photosensitizers, a 15.2 times enhancement of the CO 2 reduction rate (605.8 μmol·g −1 ·h −1 ) over that of a benchmark covalent organic framework colloid (39.9 μmol·g −1 ·h −1 ) and improved CO selectivity (98.2%) are achieved. This work presents a potential strategy for integrating optically and catalytically active centers to enhance photocatalytic CO 2 reduction.
研究领域:
材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
Science Bulletin
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2023
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IF 18.9
Canhui Zhang,Xingkun Wang,Zhentao Ma,Hanxu Yao,Hengjun Liu,Cheng Li,Jian Zhou,Ren Xu,Xusheng Zheng,Huanlei Wang,Qiang Li,Meng Gu,Heqing Jiang,Minghua Huang
Breakthrough in developing cost-effective Fe-based catalysts with superior oxygen reduction reaction (ORR) activities and ultra-long-term stability for application in Zn-air batteries (ZABs) remain a priority but still full of challenges. Herein, the neighboring NiN 4 single-metal-atom and Fe 2 N 5 dual-metal-atoms on the N-doped hollow carbon sphere (Fe/Ni-NHCS) were deliberately constructed as the efficient and robust ORR catalyst for ZABs . Both theory calculations and magnetic measurements demonstrate that the introduction of NiN 4 provides a significant role on optimizing the electron spin state of Fe 2 N 5 sites and reducing the energy barrier for the adsorption and conversion of the oxygen-containing intermediates, enabling the Fe/Ni-NHCS with excellent ORR performance and ultralow byproduct HO 2 − yield (0.5%). Impressively, the ZABs driven by Fe/Ni-NHCS exhibit unprecedented long-term rechargeable stability over 1200 h. This work paves a new venue to manipulate the spin state of active sites for simultaneously achieving superior catalytic activities and ultra-long-term stability in energy conversion technologies.
研究领域:
材料科学
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电化学
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能源技术
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
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2025
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IF 8.2
Ying Zhong,Xiao Chen,Shiyao Liu,Huibin Liu,Deng Hu,Gwendoline Lafaye,Changhai Liang
The industrial advancement of downstream products resulting from the directed hydrogenation of maleic anhydride is hindered by the limitations related to the activity and stability of catalysts. The development of nonprecious metal intermetallic compounds, in which active sites are adjustable in the local structures and electronic properties embedded within a distinct framework, holds immense potential in enhancing catalytic efficacy and stability. Herein, we report that nickel-based silicides catalysts, RNi2Si2 (R = Ca, La, and Y), afford high efficiency in the selective hydrogenation of maleic anhydride. Among the RNi2Si2 with the same tetragonal structure, CaNi2Si2 with complete isolation and highest electron density of Ni sites presents the low apparent activation energy (98.4 kJ/mol). Preferential adsorption of intermediate succinic anhydride via C═O bonds is achieved by the high oxygen affinity of CaNi2Si2, resulting in chemoselectivity to γ-butyrolactone (>80%). Additionally, the silicide with good resistance to sintering and acid corrosion presents remarkable stability for at least 130 h. The design of the silicide structure will offer fresh perspectives on the development of effective and enduring selective hydrogenation catalysts.
研究领域:
催化化学
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材料科学
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工业化学
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产品关联
DOI
PubMed
高影响因子
CHINESE JOURNAL OF CATALYSIS
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2023
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IF 16.5
Shiyao Liu,Yutong Gong,Xiao Yang,Nannan Zhang,Huibin Liu,Changhai Liang,Xiao Chen
The study of the aqueous-phase selective hydrogenation of maleic anhydride to succinic acid is important for expanding the coal chemical industry chain and promoting biomass conversion . The key lies in the development of highly efficient and stable non-noble metal catalysts. Herein, we report a novel intermetallic CaNi 2 Si 2 catalyst with high activity and stability for the aqueous-phase selective hydrogenation of maleic anhydride. The results from the experiments and theoretical calculations demonstrated that the high catalytic performance was due to the synergy of the electron-rich Ni active sites, enhanced adsorption of C=C bonds, and favorable activation of H 2 . The yield of succinic acid can be 100% over the CaNi 2 Si 2 catalyst at the contact time of 5.4 g cat /(mmol reactant ·min −1 ) under 3 MPa and 120 °C in the continuous flow reactor. Furthermore, the special coordination environment and electronic structure of Ni in CaNi 2 Si 2 inhibit the formation of carboxylates, thus enhancing the acid resistance in the reaction environment. The fine design and regulation of the structure of intermetallic silicides will be important references for the controllable optimization of maleic anhydride hydrogenation catalysts and provide new insights into the development of efficient and stable selective hydrogenation catalysts in harsh reaction environments.
研究领域:
催化化学
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材料科学
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能源化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Jin Liu,Yao Wei,Ruitao Li,Yuxin Liu,Hailing Yu,Xuan Zhou,Bo Wu,Tiejun Lin,Liangshu Zhong
Direct conversion of methane to acetic acid with high activity and selectivity over non-noble metal-based catalysts under mild reaction conditions remains a grand challenge. Specifically, 1.2Ni-ZSM-5 with 88.9 % isolated Ni sites achieved a high acetic acid yield of 2920 μ mol/g cat. and a remarkable selectivity up to 82.3 % from methane oxidative carbonylation. Combined with high angle annular dark field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy analyses, it was revealed that the isolated Ni species with Ni-O 6 moieties anchored in the micropores of ZSM-5 were suggested to be the active sites. The isotopic labeling experiments and monitoring of reaction intermediates demonstrated that CH 3 COOH was formed via the direct coupling of methyl radicals and carbon monoxide molecules. This work suggests that the well-designed Ni sites can promote the transformation of CH 4 to C 2+ oxygenates instead of traditional C 1 oxygenates as main products.
研究领域:
催化化学
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材料科学
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能源化学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Chen Qiao,Zahid Usman,Tai Cao,Souleymen Rafai,Zhitao Wang,Youqi Zhu,Chuanbao Cao,Jiatao Zhang
High-valence Ni and Fe metal sites have demonstrated a crucial role in enhancing the catalytic performances of NiFe-LDH electrocatalysts in oxygen evolution reaction (OER). Although considerable OER catalytic performances achieved under high overpotential, the catalytic talent of NiFe-LDH electrocatalysts at low overpotential is rarely realized due to the absence of high-valence Ni and Fe sites. We herein report a surface engineering route to fabricate sulfated NiFe-LDH nanosheets via ion exchange strategy in sulfate-rich media. XPS results reveal a modified surface electronic structure with high-valence Ni and Fe after ion exchange reaction. Computational PDOS results suggest that computed d-band centers (ε d ) of Fe and Ni for sulfated NiFe-LDH show a significant downward shift resulting an increased valence of metal cation with orbital volume shrinkage. The high-valence Fe can facilitate a optimized multi-electron process of Ni center from [Ni II -OH] − /[Ni III -OH] − to Ni IV -OOH rather than Ni II /Ni III to Ni IV at low overpotential. The high-valence Ni can serve as the highly active center for O-O coupling during OER process. Combined with the synergetic action of high-valence Fe and Ni, the sulfated NiFe-LDH nanosheets exhibit much larger reaction kinetics and outstanding electrocatalytic activity on glassy carbon electrode (η 10 = 219 mV, η 50 = 288 mV) with a remarkable long-term stability.
研究领域:
材料科学
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电化学
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催化科学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
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2023
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IF 6.7
Lei Fan,Yuchao Lyu,Jianye Fu,Yupeng Tian,Furang Li,Wenjing Zhang,Xinmei Liu
The prominent size effects of metal nanoparticles (NPs) are mainly reflected in the change of electronic and geometric properties, which may induce distinct catalytic performance of the catalyst. Herein, Ni/SAPO-11 bifunctional catalysts with controllable sizes of Ni NPs were synthesized to investigate the particle size effects in n-hexane hydroisomerization. The results show that decreasing Ni particle size from 11.7 to 5.3 nm increases the concentration of surface Ni atoms and the proportion of low-coordinated Ni sites (corner, step sites) by 1.7 and 1.5 times, respectively. The low-coordinated surface Ni atoms have rich dangling bonds and high surface energy, resulting in greatly improved H 2 adsorption and activation abilities. Moreover, an increased proportion of low-coordinated Ni sites within the Ni cluster shifts the d-band center upward, further enhancing the adsorption and activation of reactants. The intrinsic catalytic activity (turnover frequency) of 5.3 nm Ni NPs is ca. 2 times as much as that of the 11.7 nm ones. Besides, the smaller Ni NPs enhanced the metal–acid synergy, leading to a higher selectivity to isomers. This work provides deep insights into the metal particle size effects over the bifunctional Ni/SAPO-11 hydroisomerization catalysts and can be extended to various metal supported catalysts.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Weihao Bai,Hao Li,Gang Peng,Jinnan Wang,Aimin Li,Philippe François-Xavier Corvini
Although ferrocene (Fc) based Metal-Organic Frameworks (MOFs) can act as oxygen evolution co-catalysts (OECs) for improvement of catalytic reactivity, the poor conductivity and lack of highly active metal sites limit its further application in photoelectrochemical (PEC) water splitting. Herein, the amorphous NiFc-MOF was grafted on BiVO 4 photoanode (BiVO 4 @ a NiFc-MOFs) for efficient PEC water splitting. This novel BiVO 4 @ a NiFc-MOFs exhibits high current density of 4.34 mA cm −2 at 1.23 V RHE and relative low onset potential of 0.223 V RHE . The subsequent characterizations demonstrate that Ni species with metal-like state in bulk of a NiFc-MOFs form strong metal-support interaction with BiVO 4 , thereby promoting the interfacial charge transfer. Moreover, the surface of a NiFc-MOFs is short-range ordered with abundant coordinatively unsaturated Ni sites, creating a more favorable pathway for oxygen evolution reaction from thermodynamics. This work provides a simple method to design photoanodes with efficient OECs of amorphous MOFs for feasible PEC water splitting application.
研究领域:
材料科学
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光化学
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电化学
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催化
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产品关联
DOI
高影响因子
Science China-Chemistry
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2025
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IF 9.7
Qiu Zhuo,Dai Yiqi,Zhang Runzhi,Xiao Xin,Tong Yuqiao,Yao Lihua,Yan Dongpeng
Cost-effective metal-based electrocatalysts are desirable for industrial water and seawater electrolysis, triggering the hydrogen evolution reaction (HER) with high efficiency. Here, we report the loading of ultralow-content Ru-Os dual-atom onto NiCoP nanoneedles significantly enhancing HER in seawater splitting. The localization of 0.16% Ru and 0.58% Os atoms within NiCoP induces changes in the electronic structure and coordination environment of the Ni active sites. This catalyst achieves low overpotentials (29 and 303 mV in alkaline solution, 68 and 331 mV in alkaline seawater) at 10 and 800 mA/cm 2 , respectively, demonstrating remarkable stability by maintaining performance at 500 mA/cm 2 for 24 h in alkaline and simulated seawater. Experimental and theoretical studies indicate that ultralow content Ru and Os dual atoms are immobilized on the surface of NiCoP/NF through Ru-P and Os-P bonds, leading to electron transfer and changes in the coordination environment. These results enhance the activity of Ni active sits on support, demonstrating superior HER performance in alkaline solution and seawater. Ultralow content Ru and Os dual atoms in NiCoP@Ru-Os/NF play a crucial role in reducing the Gibbs free energy of hydrogen adsorption and lowering the d -band position of the catalyst, thereby accelerating the HER kinetic.
研究领域:
电化学
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催化
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材料科学
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能量转换
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纳米技术
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产品关联
DOI
高影响因子
ACS Applied Nano Materials
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2021
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IF 5.097
Tingting Wang,Yu Wu,Ying Han,Peiwen Xu,Yijun Pang,Xinzhen Feng,Hao Yang,Weijie Ji,Tao Cheng
Developing an efficient and low-cost electrocatalyst is important in energy conversion and storage, while it is challenging especially in the oxygen evolution reaction (OER) owing to the sluggish kinetic process. Hofmann-type metal–organic frameworks (MOFs) are layer-structured materials, and if they are synthesized in the form of regular-shaped and slim nanosheets, a higher density of exposed active sites and easier electron and mass transport will be expected. In the current study, we prepared such a type of Hofmann MOFs plus Ni site tuning for the OER. The characterizations verified the successful material synthesis and characteristics. Density functional theory (DFT) simulations proved that the Ni site modified by Fe atom is more efficient for the critical OH* as well as O* intermediate formation. Taking advantage of the designed unique structure configuration, the as-obtained Fe–Ni Hofmann-type MOF showed the OER activity with an overpotential of 290 mV at the current density of 10 mA cm–2 and a Tafel slope of 44 mV dec–1, the very best performance plus outstanding durability among the Hofmann-type MOFs for the OER known to date.
研究领域:
材料科学
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电化学
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能量转换与存储
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产品关联
DOI
高影响因子
Nature Communications
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2023
·Vol. 14
·期 1
·1-11
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IF 16.6
Chen Zhe,Li Jili,Meng Lingshen,Li Jianan,Hao Yaming,Jiang Tao,Yang Xuejing,Li Yefei,Liu Zhi-Pan,Gong Ming
Simultaneously achieving abundant and well-defined active sites with high selectivity has been one of the ultimate goals for heterogeneous catalysis. Herein, we construct a class of Ni hydroxychloride-based inorganic-organic hybrid electrocatalysts with the inorganic Ni hydroxychloride chains pillared by the bidentate N-N ligands. The precise evacuation of N-N ligands under ultrahigh-vacuum forms ligand vacancies while partially retaining some ligands as structural pillars. The high density of ligand vacancies forms the active vacancy channel with abundant and highly-accessible undercoordinated Ni sites, exhibiting 5-25 fold and 20-400 fold activity enhancement compared to the hybrid pre-catalyst and standard β-Ni(OH) 2 for the electrochemical oxidation of 25 different organic substrates, respectively. The tunable N-N ligand can also tailor the sizes of the vacancy channels to significantly impact the substrate configuration leading to unprecedented substrate-dependent reactivities on hydroxide/oxide catalysts. This approach bridges heterogenous and homogeneous catalysis for creating efficient and functional catalysis with enzyme-like properties.
研究领域:
催化
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电化学
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材料科学
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化学工程
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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）