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      Construction of Tri‐Functional HOFs Material for Efficient Selective Adsorption and Photodegradation of Bisphenol A and Hydrogen Production

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          Abstract

          This study proposes the construction of porous nanomaterial (HOFs@Fe 3+) which anchors non‐noble metal ions Fe 3+ onto nanoscale rod‐like hydrogen‐bonded organic frameworks (HOFs) by electrostatic and coordination interactions. The high specific surface area and the abundance of hydrogen‐bond adsorption active sites in pore structure of HOFs@Fe 3+ facilitate strong interactions with the double OH in bisphenol A (BPA), resulting in the highest saturation adsorption of BPA that has been reported so far (452 mg g ‐1). In addition, the ordered conjugate stacking framework structure and hydrogen bond of HOFs@Fe 3+ and the variable valence properties of Fe 3+ create new pathways for efficient separation of photogenerated carriers. The results show that HOFs@Fe 3+ can completely adsorb and photodegrade 50 ppm BPA within 20 min, owing to the abundant hydrogen bond that acts both as adsorption sites to accelerate the mass transfer process and as catalytic sites to ensure adsorption and photodegradation can be matched synergistically. Meanwhile, the efficiency of photocatalytic H 2 production by HOFs@Fe 3+ reaches 21.55 mmol g ‐1 h ‐1 with non‐noble metal Fe 3+ as co‐catalyst. This tri‐functional material with high adsorption capacity, high photodegradation efficiency, and high photocatalytic H 2 production activity can be successfully used to solve the long‐standing conflict between environment and energy.

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          Most cited references52

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          Multifunctional porous hydrogen-bonded organic framework materials

          This review provides an overview of development in the design, synthesis, and application of multifunctional porous hydrogen-bonded organic framework (HOF) materials. Hydrogen-bonded organic frameworks (HOFs) represent an interesting type of polymeric porous materials that can be self-assembled through H-bonding between organic linkers. To realize permanent porosity in HOFs, stable and robust open frameworks can be constructed by judicious selection of rigid molecular building blocks and hydrogen-bonded units with strong H-bonding interactions, in which the framework stability might be further enhanced through framework interpenetration and other types of weak intermolecular interactions such as π⋯π interactions. Owing to the reversible and flexible nature of H-bonding connections, HOFs show high crystallinity, solution processability, easy healing and purification. These unique advantages enable HOFs to be used as a highly versatile platform for exploring multifunctional porous materials. Here, the bright potential of HOF materials as multifunctional materials is highlighted in some of the most important applications for gas storage and separation, molecular recognition, electric and optical materials, chemical sensing, catalysis, and biomedicine.
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            Vapor-phase metalation by atomic layer deposition in a metal-organic framework.

            Metal-organic frameworks (MOFs) have received attention for a myriad of potential applications including catalysis, gas storage, and gas separation. Coordinatively unsaturated metal ions often enable key functional behavior of these materials. Most commonly, MOFs have been metalated from the condensed phase (i.e., from solution). Here we introduce a new synthetic strategy capable of metallating MOFs from the gas phase: atomic layer deposition (ALD). Key to enabling metalation by ALD In MOFs (AIM) was the synthesis of NU-1000, a new, thermally stable, Zr-based MOF with spatially oriented -OH groups and large 1D mesopores and apertures.
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              Functional materials discovery using energy–structure–function maps

              Molecular crystals cannot be designed like macroscopic objects because they do not assemble according to simple, intuitive rules. Their structure results from the balance of many weak interactions, unlike the strong and predictable bonding patterns found in metal–organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here, we combine computational crystal structure prediction and property prediction to build energy–structure–function maps describing the possible structures and properties available to a candidate molecule. Using these maps, we identify a highly porous solid with the lowest density reported for a molecular crystal. Both crystal structure and physical properties, such as the methane storage capacity and guest selectivity, are predicted using the molecular diagram as the only input. More generally, energy–structure–function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.
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                Author and article information

                Contributors
                Journal
                Advanced Functional Materials
                Adv Funct Materials
                1616-301X
                1616-3028
                July 2023
                April 22 2023
                July 2023
                : 33
                : 28
                Affiliations
                [1 ] College of Chemistry Chemical Engineering and Materials Science Collaborative Innovation Center of Suzhou Nano Science and Technology Soochow University Suzhou Jiangsu 215123 China
                [2 ] National Center of International Research on Intelligent New Nanomaterials and Detection Technologies in Environmental Protection Suzhou Jiangsu 215123 China
                Article
                10.1002/adfm.202300954
                4fde8b5e-8174-4e29-85f6-e793afa8378f
                © 2023

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