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.

Herein, two-dimensional (2D) TiO2 mesoporous nanosheets with three to four C3N4 layers grown in situ are employed to design a core–shell 2D/2D van der Waals heterojunction (TiO2/C3N4). Edge-terminated zero-dimensional (0D) Ti3C2 MXene quantum dots (TCQD) are subsequently integrated in the C3N4 surface via electrostatic interactions. The constructed 2D/2D/0D TiO2/C3N4/Ti3C2 composite heterojunction photocatalyst exhibits enhanced CO2 reduction activity compared to TiO2, C3N4, TiO2/C3N4, C3N4/Ti3C2 for CO and CH4 production. A step-scheme (S-scheme) charge transfer mechanism operates for the prepared samples during CO2 reduction, as authenticated by in situ X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis. This study provides a paradigm of a rational structural design for regulating the number and type of heterointerfaces and further insights into the mechanism of multijunction photocatalysts.

2D/2D/0D TiO2/C3N4/Ti3C2 MXene composite S-scheme photocatalyst with enhanced CO2 reduction activity

Photocatalysis is a green technology to use ubiquitous and intermittent sunlight. The emerging S-scheme heterojunction has demonstrated its superiority in photocatalysis. This article covers the state-of-the-art progress and provides new insights into its general designing criteria. It starts with the challenges confronted by single photocatalyst from the perspective of energy dissipation by borrowing the common behaviors in the dye molecule. Subsequently, other problems faced by single photocatalyst are summarized. Then a viable solution for these problems is the construction of heterojunctions. To overcome the problems and mistakes of type-II and Z-scheme heterojunctions, S-scheme heterojunction is proposed and the underlying reaction mechanism is summarized. Afterward, the design principles for S-scheme heterojunction are proposed and four types of S-scheme heterojunctions are suggested. Following this, direct characterization techniques for testifying the charge transfer in S-scheme heterojunction are presented. Finally, different photocatalytic applications of S-scheme heterojunctions are summarized. Specifically, this work endeavors to clarify the critical understanding on curved Fermi level in S-scheme heterojunction interface, which can help strengthen and advance the fundamental theories of photocatalysis. Moreover, the current challenges and prospects of the S-scheme heterojunction photocatalyst are critically discussed. 

Emerging S‐Scheme Photocatalyst

Inspired by natural photosynthesis, constructing inorganic/organic heterojunctions is regarded as an effective strategy to design high-efficiency photocatalysts. Herein, a step (S)-scheme heterojunction photocatalyst is prepared by in situ growth of an inorganic semiconductor firmly on an organic semiconductor. A new pyrene-based conjugated polymer, pyrene-alt-triphenylamine (PT), is synthesized via the typical Suzuki-Miyaura reactions, and then employed as a substrate to anchor CdS nanocrystals. The optimized CdS/PT composite, coupling 2 wt% PT with CdS, exhibits a robust H2 evolution rate of 9.28 mmol h-1 g-1 with continuous release of H2 bubbles, as well as a high apparent quantum efficiency of 24.3%, which is ≈8 times that of pure CdS. The S-scheme charge transfer mechanism between PT and CdS, is systematically demonstrated by photoirradiated Kelvin probe measurement and in situ irradiated X-ray photoelectron spectroscopy analyses. This work provides a protocol for preparing specific S-scheme heterojunction photocatalysts on the basis of inorganic/organic coupling.

An Inorganic/Organic S-Scheme Heterojunction H 2 -Production Photocatalyst and its Charge Transfer Mechanism

Single metal atom photocatalysts have received widespread attention due to the rational use of metal resources and maximum atom utilization efficiency. Especially N-rich amorphous g-C3N4 is always ...

Crystalline Carbon Nitride Supported Copper Single Atoms for Photocatalytic CO2 Reduction with Nearly 100% CO Selectivity

Cadmium sulfide (CdS)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption, suitable band energy levels, and excellent electronic charge transportation properties. This review focuses on the recent progress related to the design, modification, and construction of CdS-based photocatalysts with excellent photocatalytic H2 evolution performances. First, the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced. Thereafter, the fundamental properties, important advancements, and bottlenecks of CdS in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material. Subsequently, various modification strategies adopted for CdS-based photocatalysts to yield solar H2 are discussed, among which the effective approaches aim at generating more charge carriers, promoting efficient charge separation, boosting interfacial charge transfer, accelerating charge utilization, and suppressing charge-induced self-photocorrosion. The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples. Finally, the prospects and challenges encountered in developing nanostructured CdS and CdS-based nanocomposites in photocatalytic H2 evolution are presented.

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Doudou Ren

Papers

Nanostructured CdS for efficient photocatalytic H 2 evolution: A review

Strongly coupled 2D-2D nanojunctions between P-doped Ni2S (Ni2SP) cocatalysts and CdS nanosheets for efficient photocatalytic H2 evolution

In Situ Fabrication of Robust Cocatalyst-Free CdS/g-C3N4 2D–2D Step-Scheme Heterojunctions for Highly Active H2 Evolution

Highly efficient visible-light photocatalytic H2 evolution over 2D–2D CdS/Cu7S4 layered heterojunctions

Co1.4Ni0.6P cocatalysts modified metallic carbon black/g-C3N4 nanosheet Schottky heterojunctions for active and durable photocatalytic H2 production