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.
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The 5‐heterofunctionalized triazoles are important scaffolds in bioactive compounds, but current click reactions (CuAAC) cannot produce these core structures. A copper(I)‐catalyzed interrupted click ...reaction to access diverse 5‐functionalized triazoles is reported. Various 5‐amino‐, thio‐, and selenotriazoles were readily assembled in one step in high yields. The reaction proceeds under mild conditions with complete regioselectivity. It also features a broad substrate scope and good functional group compatibility.
A copper(I)‐catalyzed interrupted click reaction to access diverse 5‐functionalized triazoles is reported. Various 5‐amino‐, 5‐thio‐, and 5‐selenotriazoles were assembled in a single step in high yields. The reaction proceeds under mild conditions with complete regioselectivity and features a broad substrate scope and compatibility with various functional groups.
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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.
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An asymmetric multicomponent, interrupted Kinugasa allylic alkylation (IKAA) reaction has been developed with a synergistic Cu‐catalyzed Kinugasa system and a Pd‐catalyzed allylic alkylation ...reaction. This unprecedented reaction provides in high yields and with high stereoselectivity a synthesis of α‐quaternary chiral β‐lactams, which cannot be produced with existing synthetic methods. Stereoselective coupling of two catalytic amounts of transient organometallic intermediates formed in situ is an important feature of this reaction.
An asymmetric multicomponent interrupted Kinugasa allylic alkylation (IKAA) reaction has been developed with a synergistic Cu‐catalyzed Kinugasa and Pd‐catalyzed allylic alkylation system. This strategy provides a high yield and highly selective synthesis of α‐quaternary chiral β‐lactams, which are not easily produced by other methods. Stereoselective coupling of two transient organometallic intermediates formed in situ is the most important feature of this reaction.
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A copper(I)‐catalyzed asymmetric, three‐component interrupted Kinugasa reaction has been developed. Diverse chiral sulfur‐containing chiral β‐lactams with two consecutive stereogenic centers were ...synthesized in one step from readily available starting materials in good yields and with excellent diastereo‐ and enantioselectivity. The key is the interception of in situ formed chiral four membered copper(I) enolate intermediate with sulfur electrophiles.
A copper(I)‐catalyzed asymmetric three‐component interrupted Kinugasa reaction has been developed. Diverse chiral sulfur functional chiral β‐lactams with two consecutive stereogenic centers were synthesized in one step in good yields with excellent diastereo‐ and enantioselectivity from easily available materials.
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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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Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering ...both energy carriers (especially H2) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal‐free photocatalyst, displaying semiconductor‐like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron‐transfer efficiency and tunable light‐harvesting range (from deep UV to the near‐infrared). Here, recent advances in the rational design of CDs‐based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO2 reduction, and organic synthesis are discussed.
Carbon dots (CDs) have emerged as promising materials for various photocatalytic reactions owing to their tunable light‐harvesting range and outstanding electron‐transfer efficiency stemming from their intrinsic nanostructures. Recent advances in the rational design of CD‐based photocatalysts and their applications in photocatalytic environmental remediation, hydrogen evolution by water splitting, CO2 reduction, and organic synthesis are highlighted.
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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.
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A series of novel CoFe‐based catalysts are successfully fabricated by hydrogen reduction of CoFeAl layered‐double‐hydroxide (LDH) nanosheets at 300–700 °C. The chemical composition and morphology of ...the reaction products (denoted herein as CoFe‐x) are highly dependent on the reduction temperature (x). CO2 hydrogenation experiments are conducted on the CoFe‐x catalysts under UV–vis excitation. With increasing LDH‐nanosheet reduction temperature, the CoFe‐x catalysts show a progressive selectivity shift from CO to CH4, and eventually to high‐value hydrocarbons (C2+). CoFe‐650 shows remarkable selectivity toward hydrocarbons (60% CH4, 35% C2+). X‐ray absorption fine structure, high‐resolution transmission electron microscopy, Mössbauer spectroscopy, and density functional theory calculations demonstrate that alumina‐supported CoFe‐alloy nanoparticles are responsible for the high selectivity of CoFe‐650 for C2+ hydrocarbons, also allowing exploitation of photothermal effects. This study demonstrates a vibrant new catalyst platform for harnessing clean, abundant solar‐energy to produce valuable chemicals and fuels from CO2.
Three unique CoFe‐based catalysts are successfully fabricated via direct H2 reduction of a CoFeAl layered‐double‐hydroxide (CoFeAl‐LDH) nanosheets precursor by varying the reduction temperature. LDH precursor reduction at temperatures above 600 °C results in the formation of CoFe‐alloy nanoparticles, thereby affording a remarkable CO2 hydrogenation selectivity toward high‐value (C2+) hydrocarbons under simulated solar excitation through photothermal effects.
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