Rational Design of MOF/COF Hybrid Materials for Photocatalytic H₂ Evolution in the Presence of Sacrificial Electron Donors

Abstract

Crystalline and porous covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH -UiO-66 onto the surface of TpPa-1-COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H evolution under visible light irradiation. Especially, NH -UiO-66/TpPa-1-COF (4:6) exhibits the maximum photocatalytic H evolution rate of 23.41 mmol g h (with the TOF of 402.36 h ), which is approximately 20 times higher than that of the parent TpPa-1-COF and the best performance photocatalyst for H evolution among various MOF- and COF-based photocatalysts.

Structural Engineering of Low‐Dimensional Metal–Organic Frameworks: Synthesis, Properties, and Applications

“…Integration of MOF with other functional materials, such as other types of MOFs, [200][201][202] metal oxides, [203,204] metal NPs, [205][206][207] polyoxometalates, [208,209] covalent-organic frameworks (COFs), [210][211][212] endows the resultant MOF-based composites with improved physical and chemical properties as well as new functions. [213] Especially, previously reported LD MOF-based composites normally exhibited enhanced performances, which are arised from the successful combination of advantages of both LD MOFs and other functional materials.…”

A MOF@COF Composite with Enhanced Uptake through Interfacial Pore Generation

“…Theresulting membranes showed synergistic enhancement of selective separation of H 2 over CO 2 relative to the summed separation capacity of the MOF and COF components. [10] Herein, we present anew MOF@COF composite that we developed by confining MOF crystals in single spherical COF beads.I nt hese beads,t he MOF (UiO-66-NH 2 or Zrfumarate) crystals are dispersed into as pherical matrix made of packed nanocrystals of COF-TAPB-BTCA,atwodimensional COF assembled from two trigonal building blocks:1 ,3,5-benzenetricarbaldehyde (BTCA) and 1,3,5-tris-(4-aminophenyl)benzene (TAPB). [10] Herein, we present anew MOF@COF composite that we developed by confining MOF crystals in single spherical COF beads.I nt hese beads,t he MOF (UiO-66-NH 2 or Zrfumarate) crystals are dispersed into as pherical matrix made of packed nanocrystals of COF-TAPB-BTCA,atwodimensional COF assembled from two trigonal building blocks:1 ,3,5-benzenetricarbaldehyde (BTCA) and 1,3,5-tris-(4-aminophenyl)benzene (TAPB).…”

Covalent Organic Frameworks: Chemical Approaches to Designer Structures and Built‐In Functions

“…This high rate is attributed to the high charge mobility and better charge transfer . Covalently connecting a zirconium‐based MOF (NH 2 ‐UiO‐66) with imine‐linked COF (TpPa‐1‐COF; Figure a) yields a series of photocatalytic MOF/COF hybrids . In particular, the NH 2 ‐UiO‐66/TpPa‐1‐COF (4:6) hybrid achieves a rate of 23.41 mmol g −1 h −1 (TOF=402.36 h −1 ), thus surpassing previous MOF‐ and COF‐based photocatalysts .…”

“…[147] Covalently connecting az irconium-based MOF (NH 2 -UiO-66) with imine-linked COF (TpPa-1-COF;F igure 22 a) yields as eries of photocatalytic MOF/COF hybrids. [148] In particular, the NH 2 -UiO-66/TpPa-1-COF (4:6) hybrid achieves ar ate of 23.41 mmol g À1 h À1 (TOF = 402.36 h À1 ), thus surpassing previous MOF-and COF-based photocatalysts. [147,149] This result originates from facilitated charge separation upon covalently linking the two types of materials.R ecently,t he dibenzo-[b,d]thiophene sulfone (DBTS) based FS-COF ( Figure 33 d) with electron donor and acceptor units was developed for H 2 evolution.…”