Rational Design of Metal–Organic Framework‐Based Materials for Photocatalytic CO₂ Reduction

Abstract

Photocatalytic carbon dioxide (CO2) reduction can utilize solar light to convert CO2 to high value‐added products, which thus are recognized as an intriguing strategy to solve excessive CO2 emissions. Metal–organic framework (MOF)‐based photocatalysts have shown high potential in the field of CO2 reduction due to their high porosity and tunable structure. In this review, the recent progress achieved in the rational design of MOF‐based photocatalysts, including the pure MOF materials, MOF‐based composites, and the derivatives of MOFs, for the reduction of CO2, are summarized and the developed modification strategies to enhance the photocatalytic performance of MOF‐based photocatalysts are highlighted. The current pending issues and the outlook for the future development are also discussed.

Rational Construction of Metal Organic Framework Hybrid Assemblies for Visible Light-Driven CO2 Conversion

“…As a central part of MOF/g-C 3 N 4 composites, MOFs are easier to achieve a precise regulation of target characteristics. , The reactive sites of photocatalysts can be constructed by selecting preset organic linkers or metal cations/clusters , to achieve the purpose of adsorption and activation of CO 2 molecules via stabilizing the reaction intermediates and reducing the energy barrier. In addition, highly conjugated organic linkers like pyrene, anthracene, perylene, and porphyrin can also be conducive to the intramolecular charge-transfer process. , The introduction of functional groups (−NH 2 , −OH, etc.) into MOFs will change the chemical environment near the catalytic sites, thus further indicating the promotion of photocatalytic performance .…”

Photoreactive CO2 Capture by a Zr-Nanographene MOF

“…5 Among the materials with the highest porosity, MOFs have a high density of active surface sites available for catalysis, facile diffusion of reactants and separation of products. 6,7 Different aspects of MOF architecture including pore sizes and shapes, morphology, etc, are highly tunable with nearly infinite selection of organic or organometallic linkers and metal nodes, while post-synthetic modifications can be utilized to incorporate additional catalytic species or spectators that may orient reactants favorably or stabilize transition state structures. 8 Furthermore, the proximity and confinement of different components of a photocatalytic system-light harvester, photosensitizer, catalyst, sacrificial agent and substrate-shorten mass transfer and charge migration distances, thus improving overall efficiency.…”

“…8 Furthermore, the proximity and confinement of different components of a photocatalytic system-light harvester, photosensitizer, catalyst, sacrificial agent and substrate-shorten mass transfer and charge migration distances, thus improving overall efficiency. 6,9,10 Beginning with the first study using NH2-MIL-125(Ti) for photoreduction of carbon dioxide to HCOOin 2012, 11 MOFs and their derivatives have been actively explored in the past decade as a new class of carbon dioxide reduction photocatalyst. [6][7][8][9][10][12][13][14] This work is motivated by the need to mitigate the effects of carbon dioxide on climate change by its conversion into fuels and value-added chemicals (carbon monoxide, formic acid, methane, methanol, etc.)…”

“…6,9,10 Beginning with the first study using NH2-MIL-125(Ti) for photoreduction of carbon dioxide to HCOOin 2012, 11 MOFs and their derivatives have been actively explored in the past decade as a new class of carbon dioxide reduction photocatalyst. [6][7][8][9][10][12][13][14] This work is motivated by the need to mitigate the effects of carbon dioxide on climate change by its conversion into fuels and value-added chemicals (carbon monoxide, formic acid, methane, methanol, etc.) using sustainable energy resources, such as sunlight.…”

“…MOFs enable selective adsorption and high uptake of CO2 using functionalized or hydrophobic linkers, providing a high local concentration of CO2 around the catalytic site, while the competing hydrogen evolution reaction can be suppressed. 6 Zirconium-based MOFs are often utilized in photocatalytic CO2 reductions, because Zr-carboxylate MOFs are formed via strong coordination bonds between the Zr 4+ ions of the secondary building units (hard acid) and the carboxylate O of the ligands (hard base). 15 The stability of Zr-MOFs in organic solvents and aqueous acidic conditions combined with the abundance of Zr in nature and low toxicity of Zr in biological systems have led to growing numbers of Zr-MOFs reported in recent literature.…”