Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage

This is the peer reviewed version of the following article: Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage, which has been published in final form at https://doi.org/10.1002/anie.202010093. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Supercapacitors (SCs), showing excellent power density, long service life, and high reversibility, have received great attention because of the increasing demand for energy storage devices. To further improve their performance, it is essential to develop advanced electrode materials. One group of materials, porous crystalline solids referred to as metal-organic frameworks (MOFs), have proved to be excellent templates for synthesizing functional materials to be employed in the preparation of electrodes for SCs. In comparison to monometallic MOFs, bimetallic MOFs and their derivatives offer a number of advantages, including tunable electrochemical activity, high charge capacity, and improved electrical conductivity. This review focuses on the use of MOF-derived bimetallic materials in SCs, the origin of the improved performance, and the latest developments in the field. Furthermore, the challenges and perspectives in this research area are discussed.This work was supported by Tarbiat Modares University and College of Engineering, Peking University. Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.Sanati, S.; Abazari, R.; Albero-Sancho, J.; Morsali, A.; García Gómez, H.; Liang, Z.; Zou, R. (2021). Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage. Angewandte Chemie International Edition. 60(20):11048-11067. https://doi.org/10.1002/anie.2020100931104811067602

Hierarchical heteroaggregation of binary metal-organic gels with tunable porosity and mixed valence metal sites for removal of dyes in water

Hierarchical heteronuclear metal-organic gels (MOGs) based on iron (Fe) and aluminium (Al) metal-organic framework (MOF) backbones bridged by tri-carboxylate ligands have firstly been synthesized by simple solvothermal method. Monometallic MOGs based on Fe or Al give homogenous monoliths, which have been tuned by introduction of heterogeneity in the system (mismatched growth). The developed gels demonstrate that surface areas, pore volumes and pore sizes can be readily tuned by optimizing heterogeneity. The work also elaborates effect of heterogeneity on size of MOG particles which increase substantially with increasing heterogeneity as well as obtaining mixed valence sites in the gels. High surface areas (1861m2/g) and pore volumes (9.737cc/g) were obtained for heterogeneous gels (0.5Fe-0.5Al). The large uptakes of dye molecules (290mg/g rhodamine B and 265mg/g methyl orange) with fast sorption kinetics in both neutral and acidic mediums show good stability and accessibility of MOG channels (micro and meso-/macropores), further demonstrating their potential applications in catalysis and sorption of large molecules

High-Selective CO2 Capture in Amine-Decorated Al-MOFs

Amine-functionalized metal-organic framework (MOF) material is a promising CO2 captor in the post-combustion capture process owing to its large CO2 working capacity as well as high CO2 selectivity and easy regeneration. In this study, an ethylenediamine (ED)-decorated Al-based MOFs (named ED@MOF-520) with a high specific area and permanent porosity are prepared and evaluated to study the adsorption and separation of CO2 from N2. The results show that ED@MOF-520 adsorbent displays a superior CO2 capture performance with a CO2/N2 separation factor of 50 at 273 K, 185% times increase in the CO2/N2 separation efficiency in comparison with blank MOF-520. Furthermore, ED@MOF-520 exhibits a moderate-strength interaction with 29 kJ mol−1 adsorption heat for CO2 uptake, which not only meets the requirement of CO2 adsorption but also has good cycle stability. This work provides a promising adsorbent with a high CO2/N2 separation factor to deal with carbon peak and carbon neutrality

Rational design and synthesis of a highly porous copper-based interpenetrated metal-organic framework for high CO2 and H2 adsorption

Interpenetrated metal–organic frameworks (MOFs) are often observed to show lower porosity than their non-interpenetrating analogues. It would be highly desirable if the interpenetrated MOFs could still provide high stability, high rigidity, and optimal pore size for applications. In this work, an asymmetrical tricarboxylate organic linker was rationally designed for the construction of a copper(II)-based microporous MOF with a twofold interpenetrated structure of Pt3O4 topology. In spite of having structural interpenetration, the activated MOF shows high porosity with a Brunauer–Emmett–Teller surface area of 2297 m2g−1, and high CO2 (15.7 wt % at 273 K and 1 bar) and H2 uptake (1.64 wt % at 77 K and 1 bar)

Defect‐engineered two‐dimensional transition metal dichalcogenides towards electrocatalytic hydrogen evolution reaction

Abstract Recently, two‐dimensional transition metal dichalcogenides (TMDs) demonstrated their great potential as cost‐effective catalysts in hydrogen evolution reaction. Herein, we systematically summarize the existing defect engineering strategies, including intrinsic defects (atomic vacancy and active edges) and extrinsic defects (metal doping, nonmetal doping, and hybrid doping), which have been utilized to obtain advanced TMD‐based electrocatalysts. Based on theoretical simulations and experimental results, the electronic structure, intermediate adsorption/desorption energies and possible catalytic mechanisms are thoroughly discussed. Particular emphasis is given to the intrinsic relationship between various types of defects and electrocatalytic properties. Furthermore, current opportunities and challenges for mechanical investigations and applications of defective TMD‐based catalysts are presented. The aim herein is to reveal the respective properties of various defective TMD catalysts and provide valuable insights for fabricating high‐efficiency TMD‐based electrocatalysts

Encapsulating Trogtalite CoSe2 Nanobuds into BCN Nanotubes as High Storage Capacity Sodium Ion Battery Anodes

Trogtalite CoSe2 nanobuds encapsulated into boron and nitrogen codoped graphene (BCN) nanotubes (CoSe2@BCN-750) are synthesized via a concurrent thermal decomposition and selenization processes. The CoSe2@BCN-750 nanotubes deliver an excellent storage capacity of 580 mA h g−1 at current density of 100 mA g-1 at 100th cycle, as the anode of a sodium ion battery. The CoSe2@BCN-750 nanotubes exhibit a significant rate capability (100-2000 mA g-1 current density) and high stability (almost 98% storage retention after 4000 cycles at large current density of 8000 mA g-1). The reasons for these excellent storage properties are illuminated by theoretical calculations of the relevant models, and various possible Na+ ion storage sites are identified through first-principles calculations. These results demonstrate that the insertion of heteroatoms, B-C, N-C as well as CoSe2, into BCN tubes, enables the observed excellent adsorption energy of Na+ ions in high energy storage devices, which supports the experimental results

Titanium-based metal–organic frameworks for photocatalytic applications

Titanium-based metal–organic frameworks (Ti-MOFs) are considered one of the most appealing subclasses of the MOFs family owing to their promising optoelectronic and photocatalytic properties, high thermal and chemical stability, and unique structural features. Restricted by their challenging synthesis, however, only limited Ti-MOFs have been reported and utilized so far. In this review, we comprehensively summarize the synthesis, structures and photocatalytic applications of Ti-MOFs reported to date, particularly focusing on the synthetic strategy to develop new Ti-MOF structures and composites as photocatalysts with high sunlight harvesting efficiency and photocatalytic activity. Photocatalytic applications including photocatalytic redox reactions, water splitting, organic pollutant degradation, polymerization, deoximation reaction and sensors are highlighted. For wider interests, other applications of Ti-MOFs are also briefly introduced. This review aims to provide up-to-date developments of Ti-MOFs beneficial to researchers who currently work or are interested in this field.ASTAR (Agency for Sci., Tech. and Research, S’pore)MOE (Min. of Education, S’pore)Accepted versio

Understanding the Pathway of Gas Hydrate Formation with Porous Materials for Enhanced Gas Separation

The reason that the stoichiometry of gas to water in artificial gas hydrates formed on porous materials is much higher than that in nature is still ambiguous. Fortunately, based on our experimental thermodynamic and kinetic study on the gas hydrate formation behavior with classic ordered mesoporous carbon CMK-3 and irregular porous activated carbon combined with density functional theory calculations, we discover a microscopic pathway of the gas hydrate formation on porous materials. Two interesting processes including (I) the replacement of water adsorbed on the carbon surface by gas and (II) further replacement of water in the pore by gas accompanied with the gas condensation in the pore and growth of gas hydrate crystals out of the pore were deduced. As a result, a great enhancement of the selectivity and regeneration for gas separation was achieved by controlling the gas hydrate formation behavior accurately

Synthesis of microporous nitrogen-rich covalent-organic framework and its application in CO2 capture

An imine-based nitrogen-rich covalent-organic framework (COF) was successfully synthesized using two triangular building units under solvothermal reaction condition. The gas adsorption properties of the obtained microporous nitrogen-rich COF were investigated. The results indicated that the activated COF material presented good up take capabilities of CO2 and CH4 at 61.2 and 43.4 cm3·g−1 at 1 atm and 273 K, respectively, showing its application potential in selective gas capture and separation

Metal–Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage

This is the peer reviewed version of the following article: Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage, which has been published in final form at https://doi.org/10.1002/anie.202010093. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Supercapacitors (SCs), showing excellent power density, long service life, and high reversibility, have received great attention because of the increasing demand for energy storage devices. To further improve their performance, it is essential to develop advanced electrode materials. One group of materials, porous crystalline solids referred to as metal-organic frameworks (MOFs), have proved to be excellent templates for synthesizing functional materials to be employed in the preparation of electrodes for SCs. In comparison to monometallic MOFs, bimetallic MOFs and their derivatives offer a number of advantages, including tunable electrochemical activity, high charge capacity, and improved electrical conductivity. This review focuses on the use of MOF-derived bimetallic materials in SCs, the origin of the improved performance, and the latest developments in the field. Furthermore, the challenges and perspectives in this research area are discussed.This work was supported by Tarbiat Modares University and College of Engineering, Peking University. Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-98237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083) is gratefully acknowledged.Sanati, S.; Abazari, R.; Albero-Sancho, J.; Morsali, A.; García Gómez, H.; Liang, Z.; Zou, R. (2021). Metal-Organic Framework Derived Bimetallic Materials for Electrochemical Energy Storage. Angewandte Chemie International Edition. 60(20):11048-11067. https://doi.org/10.1002/anie.2020100931104811067602