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ACS Applied Materials & Interfaces · 2019 · IF 8.456

Stacking of Tailored Chalcogenide Nanosheets around MoO2-C Conductive Stakes Modulated by a Hybrid POM⊂MOF Precursor Template: Composite Conversion–Insertion Cathodes for Rechargeable Mg–Li Dual-Salt Batteries

Chenglong Wu,Jiulin Hu,Jing Tian,Fulu Chu,Zhenguo Yao,Yongjian Zheng,Dongguang Yin,Chilin Li

Mg anode has pronounced advantages in terms of high volumetric capacity, resource abundance, and dendrite-free electrochemical plating, which make rechargeable Mg-based batteries stand out as a representative next-generation energy storage system utilized in the field of large-scale stationary electric grid. However, sluggish Mg2+ diffusion in cathode lattices and facile passivation on the Mg anode hinder the commercialization of Mg batteries. Exploring a highly electroactive cathode prototype with hierarchical nanostructure and compatible electrolyte system with the capability of activating both an anode and a cathode is still a challenge. Here, we propose a POM⊂MOF (NENU-5) core–shell architecture as a hybrid precursor template to achieve the stacking of tailored chalcogenide nanosheets around MoO2-C conductive stakes, which can be employed as conversion–insertion cathodes (Cu1.96S-MoS2-MoO2 and Cu2Se-MoO2) for Mg–Li dual-salt batteries. Li-salt modulation further activates the capacity and rate performance at the cathode side by preferential Li-driven displacement reaction in Cu+ extrusible lattices. The heterogeneous conductive network and conformal dual-doped carbon coating enable a reversible capacity as high as 200 mAh/g with a coulombic efficiency close to 100%. The composite cathode can endure a long-term cycling up to 400 cycles and a high current density up to 2 A/g. The diversity of MOF-based materials infused by functional molecules or clusters would enrich the nanoengineering of electrodes to meet the performance demand for future multivalent batteries.

研究领域: 材料科学 · 电化学 · 能源存储
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Molecular Catalysis · 2021 · IF 5.062

Enhanced CO2 methanation activity over Ni/CeO2 catalyst by one-pot method

Rui Tang,Niamat Ullah,Yajun Hui,Xin Li,Zhenhua Li

Carbon dioxide hydrogenation for value-added chemicals has been regarded as a promising way for CO 2 utilization. This paper describes the preparation of Ni/CeO 2 catalysts derived from Ce-MOF precursor by impregnation or one-pot method and their application in carbon dioxide methanation. Various techniques were employed to characterize the prepared catalysts, including N 2 adsorption–desorption, X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (SEM), H 2 -temperature programmed reduction (H 2 -TPR), H 2 -temperature programmed desorption (H 2 -TPD) and CO 2 -temperature programmed desorption (CO 2 -TPD). The results showed that compared with commercial CeO 2 and CeO 2 prepared by precipitation, CeO 2 derived from Ce-MOF exhibited more oxygen vacancies and lower temperature reducibility, making it more beneficial for the adsorption and activation of CO 2 . Consequently, nickel supported on rod-shaped CeO 2 derived from Ce-MOF exhibited higher CO 2 conversion and methane selectivity at low temperatures. Furthermore, the Ni/CeO 2 −M-1 catalysts prepared by one-pot method showed superior activity since nickel could be partially incorporated into ceria lattice, leading to the formation of Ce 1-x Ni x O 2-y solid solutions and oxygen vacancies. The effect of nickel loading on the properties of the catalysts by one-pot method was also investigated, and the optimum Ni loading was 15 wt.% owing to the maximum number of oxygen vacancies being reached.

CAS / MDL: 554-95-0
研究领域: 催化化学 · 环境科学 · 材料科学
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CATALYSIS TODAY · 2024 · IF 5.2

Oxygen vacancy engineering in MOF-derived AuCu/ZnO bimetallic catalysts for methanol synthesis via CO2 hydrogenation

Guiming Xie,Xingyang Bai,Fei Yu,Qingyuan Yang,Zhou-jun Wang

Three AuCu/ZnO bimetallic catalysts , AuCu/ZnO-BTC, AuCu/ZnO-BDC and AuCu/ZnO-MOF-74, were derived from various MOF precursors using facile hydrothermal methods . Among the resultant catalysts, the AuCu/ZnO-BTC catalyst possessed the best methanol synthesis activity, whose space time yield of methanol ( STY MeOH ) reached 359.0 g MeOH kg cat −1 h −1 at 250 °C under 3 MPa. Structural characterization reveals that in comparison with the AuCu/ZnO-BDC and AuCu/ZnO-MOF-74 catalysts, the AuCu/ZnO-BTC catalyst possessed higher specific surface area ( S BET ), tinier metal particle size, more oxygen vacancies , stronger metal-support interactions and larger amount of medium basic sites. In situ DRIFTS result demonstrates that formate (*HCOO) species were readily generated and bridged-methoxy (*b-OCH 3 ) species were selectively formed on the AuCu/ZnO-BTC catalyst, which may be related with its abundant oxygen vacancies and responsible for its superior methanol synthesis activity. The present work derives high-performance AuCu/ZnO bimetallic catalysts from MOF precursors and provides new insight into structure-activity relationships for CO 2 hydrogenation to methanol.

研究领域: 催化化学 · 材料科学 · 环境科学
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APPLIED SURFACE SCIENCE · 2020 · IF 6.182

MOF based sheet-assembled flowers CdS-MoS2 composite for enhanced visible-light hydrogen production

Xianglei Cao,Liugen Zhang,Tingxiang Chen,Chao Feng,Zechang Liu,Ying Qi,Wei Wang,Jide Wang

MOF based CdS-MoS 2 composite had strong photoresponse and rich catalytic sites because of the adjustable morphology and large specific surface area. The CdS-MoS 2 composite was synthesized by using the first synthesized Cd-MOF as the precursor. The hydrogen evolution activity was evaluated under simulated light source. The rate of photocatalytic hydrogen production can improve by 47 times for doping 2.5% (w/w) MoS 2 compare to pure CdS. The catalyst was analyzed by the UV/vis absorption spectra, photoluminescence spectra, time-resolved photoluminescence spectra, transient photocurrent responses, electrochemical impedance spectra, Mott-Schottky test, etc. The results revealed that the CdS-MoS 2 can greatly enhance the separation and transport efficiency of photogenerated carriers, and shift the position of conduction band for the catalyst, resulting significantly improve the production of hydrogen. This work provides a new strategy for manufacturing of photocatalyst by MOFs.

研究领域: 材料科学 · 能源化学
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ENERGY & FUELS · 2023 · IF 5.3

Highly Active Porous Carbon-Supported CoNi Bimetallic Catalysts for Four-Electron Reduction of Oxygen

Changke Shao,Mingsheng Luo,Huanqiao Song,Shixin Zhang,Fengli Wang,Xinyue Liu,Zitian Huang

Great interest has been taken in oxygen reduction reaction (ORR), as a common cathode reaction in new energy sources such as fuel cells and metal–air batteries, to improve the current energy structure and develop new green energy sources. Noble metal Pt is still considered the best catalyst for this reaction. However, its disadvantages such as high cost, low selectivity, poor stability, and susceptibility to impurity poisoning severely limit its further industrial applications. Therefore, development of efficient and low-cost ORR reduction catalysts is particularly critical. M-Nx-C materials have been extensively studied to achieve a high ORR activity close to that of Pt catalysts. In this study, CoNi bimetallic alloy carbon-based oxygen reduction catalysts named CoNi-950 (Zn) were successfully synthesized, using a metal–organic framework (MOF) as a carbon precursor and a nitrogen source. The experimental results show that CoNi-950 (Zn) exhibits good ORR catalytic performance with an ultimate current density of 6.27 mA cm–2, which even exceeds that of some Pt/C catalysts with a mass loading of 20 wt % (5.92 mA cm–2). In addition, the active site of the catalyst was also identified by acid leaching and SCN– poisoning experiments, showing two sites in the form of CoNi-Nx and the CoNi alloy or its oxides in the material. Further experiments demonstrate that these two active sites have distinct ORR catalytic mechanisms, generating positive synergism in ORR. A mechanism in which O2 was catalytically reduced by CoNi-950 (Zn) in a four-electron transfer, i.e., a continuous two-step dual-electron transfer reduction process in alkaline electrolytes, is proposed.

CAS / MDL: 10026-22-9 693-98-1
研究领域: 材料科学 · 能源化学
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DALTON TRANSACTIONS · 2022 ·Vol. 51 ·期 6 ·2538-2546 · IF 4.569

Al-MOF-derived spindle-like hierarchical porous activated carbon for advanced supercapacitors

Xingyu Liu,Xiaoyue Wang,Rui Miao,Yanzhi Sun,Yongmei Chen,Yang Tang,Pingyu Wan,Junqing Pan

Metal organic frameworks (MOFs) and their derivatives have been widely used in electrochemistry due to their adjustable pore size and high specific surface area (SSA). Herein, a spindle-like hierarchical porous activated carbon (SPC) was synthesized through carbonizing the Al-BTEC precursor and then alkaline washing with NaOH. The fabricated SPC has a uniform shuttle-shaped structure, showing a large BET surface area of 1895 m2 g−1 and an average pore size of 2.4 nm. The SPC product displays a high specific capacitance (SC) of 337 F g−1 at 1 mV s−1 and 334 F g−1 at 1 A g−1. The retention of SC is about 95% after 100 000 cycles when the current density is 50 A g−1, indicating its excellent stability. Furthermore, the assembled symmetrical capacitor with a two-electrode system exhibits a high SC of 173 F g−1 at 1 A g−1 and an energy density of 15.3 W h kg−1 at a power density of 336 W kg−1. This work would provide a new pathway to design and synthesize carbon materials for supercapacitors with excellent properties in the future.

研究领域: 材料科学 · 电化学
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Nanomaterials · 2022 ·Vol. 12 ·期 9 ·1394 · IF 5.719

Copper Cobalt Sulfide Structures Derived from MOF Precursors with Enhanced Electrochemical Glucose Sensing Properties

Daojun Zhang,Xiaobei Zhang,Yingping Bu,Jingchao Zhang,Renchun Zhang

Nonenzymatic electrochemical detection of glucose is popular because of its low price, simple operation, high sensitivity, and good reproducibility. Co-Cu MOFs precursors were synthesized via the solvothermal way at first, and a series of porous spindle-like Cu-Co sulfide microparticles were obtained by secondary solvothermal sulfurization, which maintained the morphology of the MOFs precursors. Electrochemical studies exhibit that the as-synthesized Cu-Co sulfides own excellent nonenzymatic glucose detection performances. Compared with CuS, Co (II) ion-doped CuS can improve the conductivity and electrocatalytic activity of the materials. At a potential of 0.55 V, the as-prepared Co-CuS-2 modified electrode exhibits distinguished performance for glucose detection with wide linear ranges of 0.001–3.66 mM and high sensitivity of 1475.97 µA·mM−1·cm−2, which was much higher than that of CuS- and Co-CuS-1-modified electrodes. The constructed sulfide sensors derived from MOF precursors exhibit a low detection limit and excellent anti-interference ability for glucose detection.

研究领域: 材料科学 · 分析化学
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Nature Communications · 2024 ·Vol. 15 ·期 1 ·1-14 · IF 14.7

A Ce-CuZn catalyst with abundant Cu/Zn-OV-Ce active sites for CO2 hydrogenation to methanol

Ye Runping,Ma Lixuan,Mao Jianing,Wang Xinyao,Hong Xiaoling,Gallo Alessandro,Ma Yanfu,Luo Wenhao,Wang Baojun,Zhang Riguang,Duyar Melis Seher,Jiang Zheng,Liu Jian

CO 2 hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-O V -Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg cat −1 ·h −1 with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO 2 with abundant oxygen vacancies can facilitate H 2 dissociation energetically and thus improve CO 2 hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

CAS / MDL: 554-95-0
研究领域: 催化 · 化学工程 · 材料科学 · 环境科学
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