共查询到20条相似文献,搜索用时 15 毫秒
1.
Dr. Xue Feng Lu Prof. Bao Yu Xia Prof. Shuang-Quan Zang Prof. Xiong Wen Lou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4662-4678
In view of the clean and sustainable energy, metal–organic frameworks (MOFs) based materials, including pristine MOFs, MOF composites, and their derivatives are emerging as unique electrocatalysts for oxygen reduction reaction (ORR). Thanks to their tunable compositions and diverse structures, efficient MOF-based materials provide new opportunities to accelerate the sluggish ORR at the cathode in fuel cells and metal–air batteries. This Minireview first provides some introduction of ORR and MOFs, followed by the classification of MOF-based electrocatalysts towards ORR. Recent breakthroughs in engineering MOF-based ORR electrocatalysts are highlighted with an emphasis on synthesis strategy, component, morphology, structure, electrocatalytic performance, and reaction mechanism. Finally, some current challenges and future perspectives for MOF-based ORR electrocatalysts are also discussed. 相似文献
2.
Jiayue Tian Prof. Dr. Feilong Jiang Prof. Dr. Daqiang Yuan Dr. Linjie Zhang Prof. Dr. Qihui Chen Prof. Dr. Maochun Hong 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):13201-13208
Facile preparation of low-cost electrocatalysts for efficient oxygen evolution reaction (OER) remains a big challenge. Herein, a novel strategy for ultrafast (20 s) transformation of bulk metal–organic frameworks (MOFs) into ultrathin metal oxyhydroxide nanosheets for efficient OER has been developed. For two isomeric MOFs ( FJI-H25Fe and FJI-H25FeCo ), only the metastable FJI-H25FeCo bulk can immediately transform into FeCo-oxyhydroxides nanosheets through electric-field assisted hydrolysis. The potential evolution process from MOF bulk to FeCo-oxyhydroxides nanosheets has been investigated in detail. The as-made nanosheets exhibit excellent OER performances, showing an extremely low overpotential of 231 mV at the current density of 10 mA cm−2, a relatively small Tafel slope of 42 mV dec−1, and long-term durability of at least 30 h. This work not only provides a novel strategy for facile preparation of low-cost and efficient OER electrocatalysts, but also represents a new way for preparation of metal oxyhydroxides nanosheets with good crystallinity and morphology, and a fresh method for mild synthesis of nanosized derivatives from MOF materials. 相似文献
3.
Satyanarayana K. Konavarapu Debanjali Ghosh Avishek Dey Debabrata Pradhan Prof. Kumar Biradha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11141-11146
Design and synthesis of stable, active and cost-effective electrocatalyst for water splitting applications is an emerging area of research, given the depletion of fossil fuels. Herein, two isostructural NiII redox-active metal–organic frameworks (MOFs) containing flexible tripodal trispyridyl ligand ( L ) and linear dicarboxylates such as terephthalate (TA) and 2-aminoterphthalate (H2NTA) are studied for their catalytic activity in oxygen evaluation reaction (OER). The 2D-layered MOFs form 3D hydrogen bonded frameworks containing one-dimensional hydrophilic channels that are filled with water molecules. The electrochemical studies reveal that MOFs display an efficient catalytic activity towards oxygen evolution reaction in alkaline conditions with an overpotential as low as 356 mV. Further, these 2D-MOFs exhibit excellent ability to adsorb water vapor (180–230 cc g−1 at 273 K) and CO2 (33 cc g−1 at 273 K). The presence of hydrophilic functionality in the frameworks was found to significantly enhance the electrocatalytic activity as well as H2O sorption. 相似文献
4.
Hui-Li Zheng Shan-Lin Huang Ming-Bu Luo Qin Wei Er-Xia Chen Liang He Prof. Qipu Lin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23794-23798
Two novel two-dimensional metal–organic frameworks (2D MOFs), 2D-M2TCPE (M=Co or Ni, TCPE=1,1,2,2-tetra(4-carboxylphenyl)ethylene), which are composed of staggered (4,4)-grid layers based on paddlewheel-shaped dimers, serve as heterogeneous photocatalysts for efficient reduction of CO2 to CO. During the visible-light-driven catalysis, these structures undergo in situ exfoliation to form nanosheets, which exhibit excellent stability and improved catalytic activity. The exfoliated 2D-M2TCPE nanosheets display a high CO evolution rate of 4174 μmol g−1 h−1 and high selectivity of 97.3 % for M=Co and Ni, and thus are superior to most reported MOFs. The performance differences and photocatalytic mechanisms have been studied with theoretical calculations and photoelectric experiments. This study provides new insight for the controllable synthesis of effective crystalline photocatalysts based on structural and morphological coregulation. 相似文献
5.
Rui-Zhe Zhang Le-Le Lu Zhong-Hang Chen Xiaoping Zhang Bo-Yuan Wu Prof. Dr. Wei Shi Prof. Dr. Peng Cheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(28):e202200401
A cage-based metal–organic framework (Ni-NKU-101) with biphenyl-3,3’,5,5’-tetracarboxylic acid was synthesized via solvothermal method. Ni-NKU-101 contains two types of cages based on trinuclear and octa-nuclear nickel-clusters that are connected with each other by the 4-connected ligands, to form a 3D framework with a new topology. A mixed-metal strategy was used to synthesize isostructural bimetallic MOFs of MxNi1-x-NKU-101 (M=Mn, Co, Cu, Zn). The electrocatalytic studies showed that the hydrogen evolution reaction (HER) activity of CuxNi1-x-NKU-101 is much higher than that of other MxNi1-x-NKU-101 catalysts in acidic aqueous solution, owing to the synergistic effect of the bimetallic centers. The optimized Cu0.19Ni0.81-NKU-101 has an overpotential of 324 mV at 10 mA cm−2 and a Tafel slope of 131 mV dec−1. The mechanism of HER activity over these bimetallic MOF-based electrocatalysts are discussed in detail. 相似文献
6.
Dr. Shuhao An Xuewen Li Shuaishuai Shang Dr. Ting Xu Dr. Shuai Yang Dr. Cheng-Xing Cui Prof. Changjun Peng Honglai Liu Prof. Qing Xu Prof. Zheng Jiang Prof. Jun Hu 《Angewandte Chemie (International ed. in English)》2023,62(14):e202218742
Two-dimensional covalent organic frameworks (2D COFs) are often employed for electrocatalytic systems because of their structural diversity. However, the efficiency of atom utilization is still in need of improvement, because the catalytic centers are located in the basal layers and it is difficult for the electrolytes to access them. Herein, we demonstrate the use of 1D COFs for the 2e− oxygen reduction reaction (ORR). The use of different four-connectivity blocks resulted in the prepared 1D COFs displaying good crystallinity, high surface areas, and excellent chemical stability. The more exposed catalytic sites resulted in the 1D COFs showing large electrochemically active surface areas, 4.8-fold of that of a control 2D COF, and thus enabled catalysis of the ORR with a higher H2O2 selectivity of 85.8 % and activity, with a TOF value of 0.051 s−1 at 0.2 V, than a 2D COF (72.9 % and 0.032 s−1). This work paves the way for the development of COFs with low dimensions for electrocatalysis. 相似文献
7.
8.
Dr. Jun Heuk Park Dr. Jan Paczesny Namhun Kim Prof. Bartosz A. Grzybowski 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(26):10387-10391
When components of a metal–organic framework (MOF) and a crystal growth modulator diffuse through a gel medium, they can form arrays of regularly-spaced precipitation bands containing MOF crystals of different morphologies. With time, slow variations in the local concentrations of the growth modulator cause the crystals to change their shapes, ultimately resulting in unusual concave microcrystallites not available via solution-based methods. The reaction–diffusion and periodic precipitation phenomena 1) extend to various types of MOFs and also MOPs (metal–organic polyhedra), and 2) can be multiplexed to realize within one gel multiple growth conditions, in effect leading to various crystalline phases or polycrystalline formations. 相似文献
9.
Qingqing Wang Yao Zhang Dr. Huijuan Lin Prof. Jixin Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14026-14035
Considerable attention has been paid to the utilization of CO2, an abundant carbon source in nature. In this regard, porous catalysts have been eagerly explored with excellent performance for photo-/electrocatalytic reduction of CO2 to high valued products. Metal–organic frameworks (MOFs), featuring large surface area, high porosity, tunable composition and unique structural characteristics, have been widely exploited in catalytic CO2 reduction. This Minireview first reports the current progress of MOFs in CO2 reduction. Then, a specific interest is focused on MOFs in photo-/electrocatalytic reduction of CO2 by modifying their metal centers, organic linkers, and pores. Finally, the future directions of study are also highlighted to satisfy the requirement of practical applications. 相似文献
10.
Jieting Ding Danyu Guo Nanshu Wang Prof. Hao-Fan Wang Prof. Xianfeng Yang Prof. Kui Shen Prof. Liyu Chen Prof. Yingwei Li 《Angewandte Chemie (International ed. in English)》2023,62(43):e202311909
Metal–organic frameworks (MOFs) have been increasingly applied in oxygen evolution reaction (OER), and the surface of MOFs usually undergoes structural transformation to form metal oxyhydroxides to serve as catalytically active sites. However, the controllable regulation of the reconstruction process of MOFs remains as a great challenge. Here we report a defect engineering strategy to facilitate the structural transformation of MOFs to metal oxyhydroxides during OER with enhanced activity. Defective MOFs (denoted as NiFc′xFc1-x) with abundant unsaturated metal sites are constructed by mixing ligands of 1,1′-ferrocene dicarboxylic acid (Fc′) and defective ferrocene carboxylic acid (Fc). NiFc′xFc1-x series are more prone to be transformed to metal oxyhydroxides compared with the non-defective MOFs (NiFc′). Moreover, the as-formed metal oxyhydroxides derived from defective MOFs contain more oxygen vacancies. NiFc′Fc grown on nickel foam exhibits excellent OER catalytic activity with an overpotential of 213 mV at the current density of 100 mA cm−2, superior to that of undefective NiFc′. Experimental results and theoretical calculations suggest that the abundant oxygen vacancies in the derived metal oxyhydroxides facilitate the adsorption of oxygen-containing intermediates on active centers, thus significantly improving the OER activity. 相似文献
11.
Ji Hyeon Kim Dr. Siming Wu Dr. Lukas Zdrazil Nikita Denisov Prof. Patrik Schmuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(7):e202319255
In this report, a 2D MOF nanosheet derived Pd single-atom catalyst, denoted as Pd-MOF, was fabricated and examined for visible light photocatalytic hydrogen evolution reaction (HER). This Pd-MOF can provide a remarkable photocatalytic activity (a H2 production rate of 21.3 mmol/gh in the visible range), which outperforms recently reported Pt-MOFs (with a H2 production rate of 6.6 mmol/gh) with a similar noble metal loading. Notably, this high efficiency of Pd-MOF is not due to different chemical environment of the metal center, nor by changes in the spectral light absorption. The higher performance of the Pd-MOF in comparison to the analogue Pt-MOF is attributed to the longer lifetime of the photogenerated electron-hole pairs and higher charge transfer efficiency. 相似文献
12.
Taweesak Pila Dr. Prae Chirawatkul Panchanit Piyakeeratikul Vetiga Somjit Prof. Montree Sawangphruk Dr. Kanokwan Kongpatpanich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17399-17404
Deposition of redox-active metal–organic frameworks (MOFs) as thin films on conductive substrates is of great importance to improve their electrochemical performance and durability. In this work, a series of metalloporphyrinic MOF crystals was successfully deposited as thin films on carbon fiber paper (CFP) substrates, which is an alternative to rigid glass substrates. The specific dimensions of the obtained films could be adjusted easily by simple cutting. Metalloporphyrinic MOFs on CFP with different active metal species have been employed for electrochemical conversion of the carcinogenic nitrite into the less toxic nitrate. The MOFs on CFP exhibit remarkable improvement in terms of the electrocatalytic performance and reusability compared with the electrodes prepared from MOF powder. The contribution from metal species of the porphyrin units and reaction mechanisms was elucidated based on the findings from X-ray photoelectron spectroscopy (XPS) and in situ X-ray absorption near edge structure (XANES) measured during the electrochemical reaction. By integrating the redox-active property of metalloporphyrinic MOFs and high conductivity of CFP, MOF thin films on CFP provided a significant improvement of electrocatalytic performance to detoxify the carcinogenic nitrite with good stability. 相似文献
13.
Dr. Weijin Li Song Xue Sebastian Watzele Shujin Hou Johannes Fichtner A. Lisa Semrau Prof. Liujiang Zhou Dr. Alexander Welle Prof. Aliaksandr S. Bandarenka Prof. Roland A. Fischer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5886-5892
Metal–organic frameworks (MOFs) and their derivatives are considered as promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which are important for many energy provision technologies, such as electrolyzers, fuel cells and some types of advanced batteries. In this work, a “strain modulation” approach has been applied through the use of surface-mounted NiFe-MOFs in order to design an advanced bifunctional ORR/OER electrocatalyst. The material exhibits an excellent OER activity in alkaline media, reaching an industrially relevant current density of 200 mA cm−2 at an overpotential of only ≈210 mV. It demonstrates operational long-term stability even at a high current density of 500 mA cm−2 and exhibits the so far narrowest “overpotential window” ΔEORR-OER of 0.69 V in 0.1 m KOH with a mass loading being two orders of magnitude lower than that of benchmark electrocatalysts. 相似文献
14.
Dr. Ahmed A. Abdelkader Dr. Dylan D. Rodene Dr. Nazgol Norouzi Dr. Ahmed Alzharani Dr. K. Shamara Weeraratne Prof. Ram B. Gupta Prof. Hani M. El-Kaderi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(61):13896-13903
The rechargeable lithium-sulfur (Li-S) battery is a promising candidate for the next generation of energy storage technology, owing to the high theoretical capacity, high specific energy density, and low cost of electrode materials. The main drawbacks in the development of long-life Li-S batteries are capacity fading and the sluggish kinetics at the cathode caused by the polysulfides shuttle. These limitations are addressed through the design of novel nanocages containing cobalt phosphide (CoP) nanoparticles embedded in highly porous nitrogen-doped carbon (CoP-N-GC) by thermal annealing of ZIF-67 in a reductive atmosphere followed by a phosphidation step using sodium hypophosphite. The CoP nanoparticles, with large surface area and uniform homogeneous distribution within the N-doped nanocage graphitic carbon, act as electrocatalysts to suppress the shuttle of soluble polysulfides through strong chemical interactions and catalyze the sulfur redox. As a result, the S@CoP-N-GC electrode delivers an extremely high specific capacity of 1410 mA h g−1 at 0.1 C (1 C=1675 mA g−1) with an excellent coulombic efficiency of 99.7 %. Moreover, capacity retention from 864 to 678 mA h g−1 is obtained after 460 cycles with a very low decay rate of 0.046 % per cycle at 0.5 C. Therefore, the combination of the CoP catalyst and polar conductive porous carbon effectively stabilizes the sulfur cathode, enhancing the electrochemical performance and stability of the battery. 相似文献
15.
Xiaocang Han Prof. Pan Liu Dr. Fang Lin Dr. Wenqian Chen Ruichun Luo Qi Han Zhuo Jiang Prof. Xiaodong Wang Prof. Shuangxi Song Prof. Kolan Madhav Reddy Prof. Hexiang Deng Prof. Mingwei Chen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(48):21603-21608
The structural characterization of sublayer surfaces of MIL-101 is reported by low-dose spherical aberration-corrected high-resolution transmission electron microscopy (HRTEM). The state-of-the-art microscopy directly images atomic/molecular configurations in thin crystals from charge density projections, and uncovers the structures of sublayer surfaces and their evolution to stable surfaces regulated by inorganic Cr3(μ3-O) trimers. This study provides compelling evidence of metal–organic frameworks (MOFs) crystal growth via the assembly of sublayer surfaces and has important implications in understanding the crystal growth and surface-related properties of MOFs. 相似文献
16.
Hyeonbin Ha Youngik Kim Dopil Kim Jihyun Lee Yoodae Song Suyeon Kim Prof. Dr. Myung Hwan Park Prof. Dr. Youngjo Kim Hyungjun Kim Prof. Minyoung Yoon Prof. Dr. Min Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14414-14420
The effect of metal on the degree of flexibility upon evacuation of metal–organic frameworks (MOFs) has been revealed with positional control of the organic functionalities. Although Co-, Cu-, and Zn-based DMOFs (DMOF = DABCO MOF, DABCO = 1,4-diazabicyclo[2.2.2]octane) with ortho-ligands (2,3-NH2Cl) have frameworks that are inflexible upon evacuation, MOFs with para-ligands (2,5-NH2Cl) showed different N2 uptake amounts after evacuation by metal exchange. Considering that the structural analyses were not fully sufficiently different to explain the drastic changes in N2 adsorption after evacuation, quantum chemical simulation was explored. A new index (η) was defined to quantify the regularity around the metal based on differences in the oxygen-metal-oxygen angles. Within 2,5-NH2Cl, the η value becomes larger as the metal are varied from Co to Zn. A large η value means that the structures around the metal center are less ordered. These results can be used to explain flexibility changes upon evacuation by altering the metal cation in this regioisomeric system. 相似文献
17.
Hongfeng Li Peng Wu Yawen Xiao Meng Shao Yu Shen Yun Fan Huanhuan Chen Ruijie Xie Wenlei Zhang Prof. Sheng Li Prof. Jiansheng Wu Prof. Yu Fu Prof. Bing Zheng Prof. Weina Zhang Prof. Fengwei Huo 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4793-4799
Metal–organic frameworks (MOFs) are promising materials with fascinating properties. Their widespread applications are sometimes hindered by the intrinsic instability of frameworks. However, this instability of MOFs can also be exploited for useful purposes. Herein, we report the use of MOFs as metal ion precursors for constructing functional nanocomposites by utilizing the instability of MOFs. The heterogeneous growth process of nanostructures on substrates involves the release of metal ions, nucleation on substrates, and formation of a covering structure. Specifically, the synthesized CoS with carbon nanotubes as substrates display enhanced performance in a lithium-ion battery. Such strategy not only presents a new way for exploiting the instability of MOFs but also supplies a prospect for designing versatile functional nanocomposites. 相似文献
18.
Lianghao Song Tiantian Xu Daowei Gao Prof. Xun Hu Prof. Cuncheng Li Prof. Shun Li Prof. Guozhu Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6621-6627
CeO2-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO2 and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO4 to synthesize CeO2−MnO2, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO2 crystallites under a high calcination temperature and, more importantly, intimate contact within CeO2/C is conveyed to CeO2/MnO2 after the interfacial reaction; this is responsible for the high catalytic activity of CeO2−MnO2 towards CO oxidation. 相似文献
19.
David A. Burns Dr. Eric M. Press Dr. M. A. Siegler Prof. Dr. Rebekka S. Klausen Prof. Dr. V. Sara Thoi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):773-778
We report the synthesis of a set of 2D metal–organic frameworks (MOFs) constructed with organosilicon-based linkers. These oligosilyl MOFs feature linear SinMe2n(C6H4CO2H)2 ligands (lin-Sin, n=2, 4) connected by Cu paddlewheels. The stacking arrangement of the 2D sheets is dictated by van der Waals interactions and is tunable by solvent exchange, leading to reversible structural transformations between many crystalline and amorphous phases. 相似文献
20.
Dr. Jeong Hwa Song Giseong Lee Jung Heum Yoon Junyeon Jang Doosan Choi Heejun Yun Kangin Kwon Hojin Kim Prof. Dr. Chang Seop Hong Youngki Kim Prof. Dr. Hogyu Han Dr. Kwang Soo Lim Prof. Dr. Woo Ram Lee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11767-11775
Two new heterometallic metal–organic frameworks (MOFs), LnZnTPO 1 and 2 , and two homometallic MOFs, LnTPO 3 and 4 (Ln=Eu for 1 and 3 , and Tb for 2 and 4 ; H3TPO=tris(4-carboxyphenyl)phosphine oxide) were synthesized, and their structures and properties were analyzed. They were prepared by solvothermal reaction of the C3-symmetric ligand H3TPO with the corresponding metal ion(s) (a mixture of Ln3+ and Zn2+ for 1 and 2 , and Ln3+ alone for 3 and 4 ). Single-crystal XRD (SXRD) analysis revealed that 1 and 3 are isostructural to 2 and 4 , respectively. TGA showed that the framework is thermally stable up to about 400 °C for 1 and 2 , and about 450 °C for 3 and 4 . PXRD analysis showed their pore-structure distortions without noticeable framework–structure changes during drying processes. The shapes of gas sorption isotherms for 1 and 3 are almost identical to those for 2 and 4 , respectively. Solvothermal immersion of 1 and 2 in Tb3+ and Eu3+ solutions resulted in the framework metal-ion exchange affording 4 and 3 , respectively, as confirmed by photoluminescence (PL), PXRD, IR, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and energy-dispersive X-ray (EDX) analyses. 相似文献