As one of the most critical approaches to resolve the energy crisis and environmental concerns, carbon dioxide (CO2) photoreduction into value‐added chemicals and solar fuels (for example, CO, HCOOH, ...CH3OH, CH4) has attracted more and more attention. In nature, photosynthetic organisms effectively convert CO2 and H2O to carbohydrates and oxygen (O2) using sunlight, which has inspired the development of low‐cost, stable, and effective artificial photocatalysts for CO2 photoreduction. Due to their low cost, facile synthesis, excellent light harvesting, multiple exciton generation, feasible charge‐carrier regulation, and abundant surface sites, semiconductor quantum dots (QDs) have recently been identified as one of the most promising materials for establishing highly efficient artificial photosystems. Recent advances in CO2 photoreduction using semiconductor QDs are highlighted. First, the unique photophysical and structural properties of semiconductor QDs, which enable their versatile applications in solar energy conversion, are analyzed. Recent applications of QDs in photocatalytic CO2 reduction are then introduced in three categories: binary II–VI semiconductor QDs (e.g., CdSe, CdS, and ZnSe), ternary I–III–VI semiconductor QDs (e.g., CuInS2 and CuAlS2), and perovskite‐type QDs (e.g., CsPbBr3, CH3NH3PbBr3, and Cs2AgBiBr6). Finally, the challenges and prospects in solar CO2 reduction with QDs in the future are discussed.
Carbon dioxide (CO2) photoreduction is regarded as an attractive pathway to produce value‐added chemicals and fuels. Recent advances in CO2 photoreduction via semiconductor quantum dots (QDs) in three categories are reviewed: II–VI, I–III–VI, and perovskite‐type QDs. Additionally, current challenges and prospects for QD‐photocatalyzed CO2 reduction are discussed.
Inherent poor stability of perovskite nanocrystals (NCs) is the main impediment preventing broad applications of the materials. Here, TiO2 shell coated CsPbBr3 core/shell NCs are synthesized through ...the encapsulation of colloidal CsPbBr3 NCs with titanium precursor, followed by calcination at 300 °C. The nearly monodispersed CsPbBr3/TiO2 core/shell NCs show excellent water stability for at least three months with the size, structure, morphology, and optical properties remaining identical, which represent the most water‐stable inorganic shell passivated perovskite NCs reported to date. In addition, TiO2 shell coating can effectively suppress anion exchange and photodegradation, therefore dramatically improving the chemical stability and photostability of the core CsPbBr3 NCs. More importantly, photoluminescence and (photo)electrochemical characterizations exhibit increased charge separation efficiency due to the electrical conductivity of the TiO2 shell, hence leading to an improved photoelectric activity in water. This study opens new possibilities for optoelectronic and photocatalytic applications of perovskites‐based NCs in aqueous phase.
TiO2 shell coated CsPbBr3 core/shell nanocrystals are successfully constructed, resulting in excellent water, photo and thermal stability. TiO2 shell coating effectively increases charge separation efficiency, hence leading to an improved photoelectric activity in water.
Photo/electrocatalytic ammonia synthesis has recently developed fast while the ammonia yields over state‐of‐the‐art photo/electrocatalysts are still very moderate. Such low concentration of ...synthesized NH3 brings about a challenge to the reliable quantification of the product in photo/electrocatalysis. Notably, we found that the quantitative detection of ammonia concentration below 0.2 ppm is error‐prone, which is likely the case happening in the majority of photo/electrocatalytic NH3 synthesis, thus arising concerns about the rationality and accuracy for low‐concentration ammonia quantification in these processes. Herein, we discuss the methodology used and analyze the reliability of various detection methods for the detection of trace ammonia in aqueous media. The challenges facing the detection of low concentration of ammonia in photo/electrocatalysis can be overcome by integration with multiple detection methods. According to the data presented, we also propose an effective criterion for precise quantification of ammonia, avoiding the unreasonable comparisons in photo/electrocatalytic ammonia synthesis.
The analytical methods for the detection of ammonia concentration below 0.2 ppm in photo/electrocatalytic N2 fixation are evaluated rigorously, reliably, and insightfully. The low‐concentration ammonia quantification minefield was indicated and a rigorous ammonia detection flowchart as well as another reference standard to achieve a more accurate and responsible ammonia detection in photo/electrocatalysis was concluded.
Covalent organic frameworks have recently gained increasing attention in photocatalytic hydrogen generation from water. However, their structure-property-activity relationship, which should be ...beneficial for the structural design, is still far-away explored. Herein, we report the designed synthesis of four isostructural porphyrinic two-dimensional covalent organic frameworks (MPor-DETH-COF, M = H
, Co, Ni, Zn) and their photocatalytic activity in hydrogen generation. Our results clearly show that all four covalent organic frameworks adopt AA stacking structures, with high crystallinity and large surface area. Interestingly, the incorporation of different transition metals into the porphyrin rings can rationally tune the photocatalytic hydrogen evolution rate of corresponding covalent organic frameworks, with the order of CoPor-DETH-COF < H
Por-DETH-COF < NiPor-DETH-COF < ZnPor-DETH-COF. Based on the detailed experiments and calculations, this tunable performance can be mainly explained by their tailored charge-carrier dynamics via molecular engineering. This study not only represents a simple and effective way for efficient tuning of the photocatalytic hydrogen evolution activities of covalent organic frameworks at molecular level, but also provides valuable insight on the structure design of covalent organic frameworks for better photocatalysis.
Catalytic C1 chemistry based on the activation/conversion of synthesis gas (CO+H2), methane, carbon dioxide, and methanol offers great potential for the sustainable development of hydrocarbon fuels ...to replace oil, coal, and natural gas. Traditional thermal catalytic processes used for C1 transformations require high temperatures and pressures, thereby carrying a significant carbon footprint. In comparison, solar‐driven C1 catalysis offers a greener and more sustainable pathway for manufacturing fuels and other commodity chemicals, although conversion efficiencies are currently too low to justify industry investment. In this Review, we highlight recent advances and milestones in light‐driven C1 chemistry, including solar Fischer–Tropsch synthesis, the water‐gas‐shift reaction, CO2 hydrogenation, as well as methane and methanol conversion reactions. Particular emphasis is placed on the rational design of catalysts, structure–reactivity relationships, as well as reaction mechanisms. Strategies for scaling up solar‐driven C1 processes are also discussed.
Soaking up the sun: This Review highlights recent achievements in solar‐driven C1 chemistry, especially in processes such as solar‐driven Fischer–Tropsch synthesis, the water‐gas‐shift reaction, CO2 hydrogenation, as well as CH4 and CH3OH conversion. Particular emphasis is placed on the rational design of catalysts, structure–reactivity relationships, as well as reaction mechanisms during the solar‐driven processes.
Eosin Y, a well‐known economical alternative to metal catalysts in visible‐light‐driven single‐electron transfer‐based organic transformations, can behave as an effective direct hydrogen‐atom ...transfer catalyst for C−H activation. Using the alkylation of C−H bonds with electron‐deficient alkenes as a model study revealed an extremely broad substrate scope, enabling easy access to a variety of important synthons. This eosin Y‐based photocatalytic hydrogen‐atom transfer strategy is promising for diverse functionalization of a wide range of native C−H bonds in a green and sustainable manner.
Neutral eosin Y has been employed as an effective direct hydrogen‐atom transfer photocatalyst to activate a wide range of native C−H bonds in a green and sustainable fashion. This transformation is distinguished by its operational simplicity and amenability to large‐scale synthesis using continuous‐flow technology (EWG=aldehyde, ketone, ester, amide, imide, cyanide, sulfone, nitro, pyridine).
In recent years, visible-light-driven organic reactions have been experiencing a significant renaissance in response to topical interest in environmentally friendly green chemical synthesis. The ...transformations using inexpensive, readily available visible-light sources have come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In this review, we focus on recent advances in the development of visible-light-driven organic reactions, including aerobic oxidation, hydrogen-evolution reactions, energy-transfer reactions and asymmetric reactions. These key research topics represent a promising strategy towards the development of practical, scalable industrial processes with great environmental benefits.
Graphdiyne (GDY) with a direct band gap, excellent carrier mobility and uniform pores, is regarded as a promising photocatalytic material for solar energy conversion, while the research on GDY in ...photocatalysis is a less developed field. Herein, the distinctive structure, adjustable band gap, and electronic properties of GDY for photocatalysis is firstly summarized. The construction and progress of GDY‐based photocatalysts for solar energy conversion, including H2 evolution reaction (HER), CO2 reduction reaction (CO2RR) and N2 reduction reaction (NRR) are then elaborated. At last, the challenges and perspectives in developing GDY‐based photocatalysts for solar fuel production are discussed. It is anticipated that a timely Minireview will be helpful for rapid progress of GDY in solar energy conversion.
Because of their large specific surface area, adjustable band gap, and uniformly pore structure, graphdiyne (GDY) materials have become a rising star for photocatalytic energy conversion. This Minireview summarizes the unique physicochemical properties of GDY as well as the construction and progress of GDY‐based photocatalysts for hydrogen evolution, CO2 reduction and nitrogen reduction.
Light‐driven multielectron redox reactions (e.g., hydrogen (H2) evolution, CO2 reduction) have recently appeared at the front of solar‐to‐fuel conversion. In this Minireview, we focus on the recent ...advances in establishing semiconductor quantum dot (QD) assemblies to enhance the efficiencies of these light‐driven multielectron reduction reactions. Four models of QD assembly are established to promote the sluggish kinetics of multielectron transfer from QDs to cocatalysts, thus leading to an enhanced activity of solar H2 evolution or CO2 reduction. We also forecast the potential applications of QD assemblies in other multielectron redox reactions, such as nitrogen (N2) fixation and oxygen (O2) evolution from H2O.
Join the dots: This Minireview focuses on the recent advances in constructing semiconductor quantum dot (QD) assemblies to enhance the efficiencies of light‐driven multielectron redox reactions, such as H2 evolution and CO2 reduction. Furthermore, their potential applications in N2 fixation and H2O oxidation is suggested.
Nitrogen‐doped porous carbon nanosheets (N‐CNS) are synthesized by hydrothermal carbon coating of g‐C3N4 nanosheets followed by high‐temperature treatment in N2. g‐C3N4 serves as a template, nitrogen ...source, and porogen in the synthesis. This approach yields N‐CNS with a high nitrogen content and comparable oxygen reduction reaction catalytic activities to commercial Pt/C catalysts in alkaline media.
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