Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.

Cocatalysts for Selective Photoreduction of CO2 into Solar Fuels.

Composite Photocatalysts Nan Zhang,†,‡ Min-Quan Yang,†,‡ Siqi Liu,†,‡ Yugang Sun,* and Yi-Jun Xu*,†,‡ †State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350002, P.R. China ‡College of Chemistry, New Campus, Fuzhou University, Fuzhou 350108, P.R. China Center for Nanoscale Materials, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States

Waltzing with the Versatile Platform of Graphene to Synthesize Composite Photocatalysts.

Replacement of part of the fossil fuel consumption by renewable energy, in particular in the chemical industry, is a central strategy for resource and energy efficiency. This perspective will show that CO2 is the key molecule to proceed effectively in this direction. The routes, opportunities and barriers in increasing the share of renewable energy by using CO2 reaction and their impact on the chemical and energy value chains are discussed after introducing the general aspects of this topic evidencing the tight integration between the CO2 use and renewable energy insertion in the value chain of the process industry. The focus of this perspective article is on the catalytic aspects of the chemistries involved, with an analysis of the state-of-the-art, perspectives and targets to be developed. The reactions discussed are the production of short-chain olefins (ethylene, propylene) from CO2, and the conversion of carbon dioxide to syngas, formic acid, methanol and dimethyl ether, hydrocarbons via Fischer–Tropsch synthesis and methane. The relevance of availability, cost and environmental footprints of H2 production routes using renewable energies is addressed. The final part discusses the possible scenario for CO2 as an intermediary for the incorporation of renewable energy in the process industry, with a concise roadmap for catalysis needs and barriers to reach this goal.

Catalysis for CO2 conversion: a key technology for rapid introduction of renewable energy in the value chain of chemical industries

As a promising approach to achieving two objectives with one strategy, photocatalytic CO2 conversion for C1/C2 “solar fuels” production can provide a package solution to the current global warming and growing energy demand by using inexhaustible solar energy and increasing atmospheric CO2. Although numerous efforts have been made to enhance the CO2 conversion efficiency through developing photocatalysts and CO2 reduction systems in recent years, some challenges still remain in improving the activity and selectivity of the CO2 photoreduction reactions. This review gives an overview of fundamental aspects and recent research advances of heterogeneous photocatalytic CO2 conversion systems in the last 3 years, and the catalysts are categorized as one-step excitation semiconductor systems, one-step excitation photosensitized semiconductor systems, and two-step excitation hybrid systems such as semiconductor heterojunction and Z-scheme systems. Also, some suggestions are given for further confirming that the ca...

Recent Advances in Heterogeneous Photocatalytic CO2 Conversion to Solar Fuels

In recent years, heterogeneous photocatalysis has received much research interest because of its powerful potential applications in tackling many important energy and environmental challenges at a global level in an economically sustainable manner. Due to their unique optical, electrical, and physicochemical properties, various 2D graphene nanosheets-supported semiconductor composite photocatalysts have been widely constructed and applied in different photocatalytic fields. In this review, fundamental mechanisms of heterogeneous photocatalysis, including thermodynamic and kinetics requirements, are first systematically summarized. Then, the photocatalysis-related properties of graphene and its derivatives, and design rules and synthesis methods of graphene-based composites are highlighted. Importantly, different design strategies, including doping and sensitization of semiconductors by graphene, improving electrical conductivity of graphene, increasing eloectrocatalytic active sites on graphene, strengthening interface coupling between semiconductors and graphene, fabricating micro/nano architectures, constructing multi-junction nanocomposites, enhancing photostability of semiconductors, and utilizing the synergistic effect of various modification strategies, are thoroughly summarized. The important applications including photocatalytic pollutant degradation, H2 production, and CO2 reduction are also addressed. Through reviewing the significant advances on this topic, it may provide new opportunities for designing highly efficient 2D graphene-based photocatalysts for various applications in photocatalysis and other fields, such as solar cells, thermal catalysis, separation, and purification.

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Graphene in Photocatalysis: A Review

The photocatalyst–enzyme coupled system for artificial photosynthesis process is one of the most promising methods of solar energy conversion for the synthesis of organic chemicals or fuel. Here we report the synthesis of a novel graphene-based visible light active photocatalyst which covalently bonded the chromophore, such as multianthraquinone substituted porphyrin with the chemically converted graphene as a photocatalyst of the artificial photosynthesis system for an efficient photosynthetic production of formic acid from CO2. The results not only show a benchmark example of the graphene-based material used as a photocatalyst in general artificial photosynthesis but also the benchmark example of the selective production system of solar chemicals/solar fuel directly from CO2.

A Photocatalyst–Enzyme Coupled Artificial Photosynthesis System for Solar Energy in Production of Formic Acid from CO2

The successful development of a photocatalyst/biocatalyst integrated system that carries out selective methanol production from CO2 is reported herein. The fine-tuned system was derived from a judicious combination of graphene-based visible light active photocatalyst (CCG-IP) and sequentially coupled enzymes. The covalent attachment of isatin-porphyrin (IP) chromophore to chemically converted graphene (CCG) afforded newly developed CCG-IP photocatalyst for this research endeavor. The current work represents a new benchmark for carrying out highly selective methanol formation from CO2 in an environmentally benign manner.

Highly selective solar-driven methanol from CO2 by a photocatalyst/biocatalyst integrated system.

The utilization of CO2 for production of solar fuels/chemicals is gaining increasing importance due to worldwide fossil-fuel shortage and global warming. As a means to achieve this, we herein report on the synthesis and development of a graphene-based visible light active photocatalyst (CCG–BODIPY) which is chemically converted graphene (CCG) covalently bonded to a light harvesting BODIPY molecule (1-picolylamine-2-aminophenyl-3-oxy-phenyl-4,4′-difluoro-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene-triazine). The photocatalyst-biocatalyst coupled system developed using CCG–BODIPY as photocatalyst functions in a highly efficient manner, leading to high NADH regeneration (54.02 ± 0.61%), followed by its consumption in exclusive formic acid production (144.2 ± 1.8 μmol) from CO2. The present research endeavour highlights the development and application of a graphene based photocatalyst for direct solar fuel formation from carbon dioxide.

Gyu Hwan Oh

Papers

A Photocatalyst–Enzyme Coupled Artificial Photosynthesis System for Solar Energy in Production of Formic Acid from CO2

Highly selective solar-driven methanol from CO2 by a photocatalyst/biocatalyst integrated system.

Graphene–BODIPY as a photocatalyst in the photocatalytic–biocatalytic coupled system for solar fuel production from CO2