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      Unraveling Charge‐Separation Mechanisms in Photocatalyst Particles by Spatially Resolved Surface Photovoltage Techniques

      1 , 1 , 1
      Angewandte Chemie
      Wiley

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          Abstract

          The photocatalytic conversion of solar energy offers a potential route to renewable energy, and its efficiency relies on effective charge separation in nanostructured photocatalysts. Understanding the charge‐separation mechanism is key to improving the photocatalytic performance and this has now been enabled by advances in the spatially resolved surface photovoltage (SRSPV) method. In this Review we highlight progress made by SRSPV in mapping charge distributions at the nanoscale and determining the driving forces of charge separation in heterogeneous photocatalyst particles. We discuss how charge separation arising from a built‐in electric field, diffusion, and trapping can be exploited and optimized through photocatalyst design. We also highlight the importance of asymmetric engineering of photocatalysts for effective charge separation. Finally, we provide an outlook on further opportunities that arise from leveraging these insights to guide the rational design of photocatalysts and advance the imaging technique to expand the knowledge of charge separation.

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          Most cited references121

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          Heterojunction Photocatalysts.

          Semiconductor-based photocatalysis attracts wide attention because of its ability to directly utilize solar energy for production of solar fuels, such as hydrogen and hydrocarbon fuels and for degradation of various pollutants. However, the efficiency of photocatalytic reactions remains low due to the fast electron-hole recombination and low light utilization. Therefore, enormous efforts have been undertaken to solve these problems. Particularly, properly engineered heterojunction photocatalysts are shown to be able to possess higher photocatalytic activity because of spatial separation of photogenerated electron-hole pairs. Here, the basic principles of various heterojunction photocatalysts are systematically discussed. Recent efforts toward the development of heterojunction photocatalysts for various photocatalytic applications are also presented and appraised. Finally, a brief summary and perspectives on the challenges and future directions in the area of heterojunction photocatalysts are also provided.
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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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              Particulate photocatalysts for overall water splitting

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                Author and article information

                Contributors
                Journal
                Angewandte Chemie
                Angewandte Chemie
                Wiley
                0044-8249
                1521-3757
                April 11 2022
                February 21 2022
                April 11 2022
                : 134
                : 16
                Affiliations
                [1 ] State Key Laboratory of Catalysis Dalian National Laboratory for Clean Energy Dalian Institute of Chemical Physics Chinese Academy of Sciences Zhongshan Road 457 Dalian 116023 China
                Article
                10.1002/ange.202117567
                4269604b-ff84-4bec-aa00-dcf7ae24ac4d
                © 2022

                http://onlinelibrary.wiley.com/termsAndConditions#vor

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