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      CO 2 Reduction: From the Electrochemical to Photochemical Approach

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          Abstract

          Increasing CO 2 concentration in the atmosphere is believed to have a profound impact on the global climate. To reverse the impact would necessitate not only curbing the reliance on fossil fuels but also developing effective strategies capture and utilize CO 2 from the atmosphere. Among several available strategies, CO 2 reduction via the electrochemical or photochemical approach is particularly attractive since the required energy input can be potentially supplied from renewable sources such as solar energy. In this Review, an overview on these two different but inherently connected approaches is provided and recent progress on the development, engineering, and understanding of CO 2 reduction electrocatalysts and photocatalysts is summarized. First, the basic principles that govern electrocatalytic or photocatalytic CO 2 reduction and their important performance metrics are discussed. Then, a detailed discussion on different CO 2 reduction electrocatalysts and photocatalysts as well as their generally designing strategies is provided. At the end of this Review, perspectives on the opportunities and possible directions for future development of this field are presented.

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          Most cited references225

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          Roles of cocatalysts in photocatalysis and photoelectrocatalysis.

          Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.
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            Aqueous CO2 reduction at very low overpotential on oxide-derived Au nanoparticles.

            Carbon dioxide reduction is an essential component of many prospective technologies for the renewable synthesis of carbon-containing fuels. Known catalysts for this reaction generally suffer from low energetic efficiency, poor product selectivity, and rapid deactivation. We show that the reduction of thick Au oxide films results in the formation of Au nanoparticles ("oxide-derived Au") that exhibit highly selective CO(2) reduction to CO in water at overpotentials as low as 140 mV and retain their activity for at least 8 h. Under identical conditions, polycrystalline Au electrodes and several other nanostructured Au electrodes prepared via alternative methods require at least 200 mV of additional overpotential to attain comparable CO(2) reduction activity and rapidly lose their activity. Electrokinetic studies indicate that the improved catalysis is linked to dramatically increased stabilization of the CO(2)(•-) intermediate on the surfaces of the oxide-derived Au electrodes.
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              Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide.

              In view of the climate changes caused by the continuously rising levels of atmospheric CO2 , advanced technologies associated with CO2 conversion are highly desirable. In recent decades, electrochemical reduction of CO2 has been extensively studied since it can reduce CO2 to value-added chemicals and fuels. Considering the sluggish reaction kinetics of the CO2 molecule, efficient and robust electrocatalysts are required to promote this conversion reaction. Here, recent progress and opportunities in inorganic heterogeneous electrocatalysts for CO2 reduction are discussed, from the viewpoint of both experimental and computational aspects. Based on elemental composition, the inorganic catalysts presented here are classified into four groups: metals, transition-metal oxides, transition-metal chalcogenides, and carbon-based materials. However, despite encouraging accomplishments made in this area, substantial advances in CO2 electrolysis are still needed to meet the criteria for practical applications. Therefore, in the last part, several promising strategies, including surface engineering, chemical modification, nanostructured catalysts, and composite materials, are proposed to facilitate the future development of CO2 electroreduction.
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                Author and article information

                Contributors
                yanguang@suda.edu.cn
                Journal
                Adv Sci (Weinh)
                Adv Sci (Weinh)
                10.1002/(ISSN)2198-3844
                ADVS
                Advanced Science
                John Wiley and Sons Inc. (Hoboken )
                2198-3844
                12 September 2017
                November 2017
                : 4
                : 11 ( doiID: 10.1002/advs.v4.11 )
                : 1700194
                Affiliations
                [ 1 ] Institute of Functional Nano and Soft Materials (FUNSOM) Jiangsu Key Laboratory for Carbon‐Based Functional Materials and Devices Soochow University Suzhou 215123 China
                Author notes
                Author information
                http://orcid.org/0000-0003-0506-0451
                Article
                ADVS392
                10.1002/advs.201700194
                5700640
                9007bda6-1e1d-4e19-a7e9-88a773702370
                © 2017 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim

                This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

                History
                : 28 April 2017
                : 02 July 2017
                Page count
                Figures: 20, Tables: 3, Pages: 29, Words: 22748
                Funding
                Funded by: Ministry of Science and Technology of China
                Award ID: 2017YFA0204800
                Funded by: National Natural Science Foundation of China
                Award ID: 51472173
                Award ID: 51522208
                Funded by: Natural Science Foundation of Jiangsu Province
                Award ID: BK20140302
                Award ID: SBK2015010320
                Funded by: Priority Academic Program Development of Jiangsu Higher Education Institutions, Collaborative Innovation Center of Suzhou Nano Science and Technology
                Categories
                Review
                Reviews
                Custom metadata
                2.0
                advs392
                November 2017
                Converter:WILEY_ML3GV2_TO_NLMPMC version:5.2.6.1 mode:remove_FC converted:23.11.2017

                co2 reduction,electrocatalysis,nanotechnology,photocatalysis

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