Atomically Dispersed Metal Sites in MOF‐Based Materials for Electrocatalytic and Photocatalytic Energy Conversion

Abstract

Metal sites play an essential role in both electrocatalytic and photocatalytic energy conversion. The highly ordered arrangements of the organic linkers and metal nodes as well as the well-defined pore structures of metal-organic frameworks (MOFs) make them ideal substrates to support atomically dispersed metal sites (ADMSs) located in their metal nodes, linkers, and pores. Porous carbon materials doped with ADMSs can be derived from these ADMS-incorporating MOF precursors through controlled treatments. These ADMSs incorporated in pristine MOFs and MOF-derived carbon materials possess unique advantages over molecular or bulk metal-based catalysts and bridge the gap between homogeneous and heterogeneous catalysts for energy-conversion applications. This Review presents recent progress in the design and incorporation of ADMSs in MOFs and MOF-derived materials for energy-conversion applications.

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO

“…[1a,2] To date,m uch research has been devoted to developing selective catalysts for reduction of CO 2 to CO. [3] Precious metals have been identified as promising candidates for CO 2 reduction to CO but their practical applications are still limited. [10,11] In contrast, no Cu-based catalysts with single active sites have been developed for the photocatalytic CO 2 reduction. [5] To date,v arious Cu-based catalysts have been developed but limited product selectivity due to the presence of multiple neighboring sites for involving CO 2 reduction.…”

“…To enhance product selectivity,aconventional approach is to tailor the number of nearest neighboring accessible Cu atoms,s uch as reducing the particle size [6] or hybridizing Cu with other metals. [10,11] In contrast, no Cu-based catalysts with single active sites have been developed for the photocatalytic CO 2 reduction. [8] In particular,t he presence of unsaturated coordinated single active sites or defect can modify the electron structure of catalysts,w hich could stabilize the reaction intermediates and thus depress the energy barrier of the photoreduction CO 2 .…”

“…[7] Besides these,i ntroducing single active site in ac atalyst has been proven to be an effective strategy to study the reactive pathway and enhance the activity for CO 2 reduction reaction (CO2RR). [10,11] In contrast, no Cu-based catalysts with single active sites have been developed for the photocatalytic CO 2 reduction. [9] Recent studies demonstrate that this type of catalyst exhibits high activity for reducing CO 2 to CO. [10] However, such ac atalyst is generally obtained through pyrolysis of Ni, or Co-based metal-organic frameworks (MOFs) or coordination polymers.…”

Pore‐Surface Engineering by Decorating Metal‐Oxo Nodes with Phenylsilane to Give Versatile Super‐Hydrophobic Metal–Organic Frameworks (MOFs)

“…In contrast to the previous reports,w hich mainly focused on the modification of organic ligands in MOFs,h erein, we reported an ovel strategy to decorate the metal-oxo nodes of MOFs with phenylsilane to affords uper-hydrophobic NH 2 -UiO-66(Zr), which shows highly improved base resistance and holds great promise in versatile applications,s uch as organic/water separation, selfcleaning,a nd liquid-marble fabrication. [5][6][7][8][9][10][11][12][13] Recent research has involved preparing hydrophobic MOFs,n ot only to combat their failure in applications under humid conditions,b ut also endow them with improved or even novel functional properties. [1,2] Super-hydrophobic porous materials are of interest since they can provide both aw ater-repellent surface and inherent porosity,w hich enable them to be used for some special applications,s uch as contaminatedwater treatments and fuel purification.…”

“…[1,2] Super-hydrophobic porous materials are of interest since they can provide both aw ater-repellent surface and inherent porosity,w hich enable them to be used for some special applications,s uch as contaminatedwater treatments and fuel purification. [5][6][7][8][9][10][11][12][13] Recent research has involved preparing hydrophobic MOFs,n ot only to combat their failure in applications under humid conditions,b ut also endow them with improved or even novel functional properties. [5][6][7][8][9][10][11][12][13] Recent research has involved preparing hydrophobic MOFs,n ot only to combat their failure in applications under humid conditions,b ut also endow them with improved or even novel functional properties.…”