Epoxides boast intrinsic ring strain and high reactivity towards various nucleophiles, thus rendering them fundamental building blocks in organic synthesis. Notably, the ring-opening of these readily available compounds offers a versatile strategy to produce a diverse array of valuable functionalized molecules, such as alcohols, carboxylic acids, olefins, etc. However, the conventional reaction systems for ring-opening typically rely on harmful agents or harsh conditions, which limit their applicability in complex molecule synthesis. Recent advancements in photocatalysis have emerged as a sustainable and promising alternative for precise cleavage of strained C−O bonds in epoxides under mild conditions, showcasing rapid development over the past decade. This mini-review examines the mechanisms and strategies for regioselective epoxide ring-opening triggered by varieties of nucleophiles based on photocatalysis, encompassing fundamental concepts of ring-opening, key factors influencing product regioselectivity and the potential impact of operando techniques and artificial intelligence on this field. The persistent challenges and potential trajectory in this dynamic domain are also critically discussed to foster further innovation.

Photocatalytic nonoxidative coupling of methane (CH4, NOCM) to ethane (C2H6) is a promising route for CH4 valorization, yet its efficient implementation requires the seamless coordination of CH4 adsorption, C-H bond activation, and C-C coupling. This intrinsic complexity makes it fundamentally challenging for a single type of active site to drive the entire NOCM process efficiently. Herein, we induce the formation of Ce3+ sites on the surface of CeO2 by loading Ag nanoparticles (NPs) for NOCM, and achieve highly efficient and selective conversion of CH4 to C2H6. Mechanistic studies indicate that the Ce3+ sites enhance CH4 adsorption and facilitate C-H bond activation to generate methyl radicals (˙CH3). Subsequently, Ag NPs promote the coupling of ˙CH3, ultimately producing C2H6. This study presents a synergistic catalysis strategy for designing efficient photocatalysts to achieve the selective coupling of CH4 into higher-value chemicals.

The sluggish water oxidation kinetics limit photocatalytic H2O2 production. We overcome this by coupling two-electron oxygen reduction (2e- ORR) with selective 1,2,3,4-tetrahydroisoquinoline (THIQ) oxidation over an rGO-CdS photocatalyst, achieving efficient coproduction of H2O2 and 3,4-dihydroisoquinoline (DHIQ). This cooperative photoredox strategy enables sustainable synthesis of value-added chemicals.

Catalytic coupling of abundant CO2 or renewable CH3OH with nitrogenous small molecules, such as N2, NH3, and NO3−, has emerged as a promising strategy for synthesizing high-value organonitrogen compounds. However, conventional thermal catalysis for C–N bond formation often relies on external chemical reagents and energy-intensive conditions, raising concerns about process sustainability. Photocatalysis offers a sustainable alternative by utilizing sunlight to generate high-energy electron-hole pairs in semiconductors, which can activate inert chemical bonds (e.g., C=O and N≡N) for programmed coupling under ambient conditions. In this review, we dissect the fundamental activation mechanisms underlying photon-mediated C‒N coupling reactions, highlight key recent breakthroughs in the synthesis of urea, formamide, and amino acids, and analyze persistent challenges alongside emerging opportunities. This work aims to deepen the understanding of photocatalytic C–N coupling reactions and inspire research interest in sustainable nitrogen fixation and carbon utilization.

The functionalization of methane is regarded as the "holy grail" reaction in chemistry. Photocatalysis is an emerging approach that activates the inert C-H bond in methane under mild conditions, enabling its functionalization to produce sustainable chemicals. However, achieving selective C-H functionalization remains a significant challenge due to methane's "chameleon-like" behavior under diverse reaction conditions. In this review, we provide a comprehensive overview of recent advances in heterogeneous photocatalytic methane functionalization, covering the fundamental principles of photocatalysis and various synthetic systems, with an emphasis on the mechanisms underlying the structure-activity relationships of the microscopic structure of photocatalysts and the reactions. The potential future applications of artificial intelligence and machine learning in developing efficient methane functionalization systems are also highlighted, aiming to guide future research.

The photocatalytic conversion of methane (CH4) into high-value multicarbon (C2+) products under ambient conditions provides a highly promising approach for the transformation of the energy structure and environmental protection. However, the high C-H bond dissociation energy of CH4 and the overoxidation of methyl radical (˙CH3) intermediates greatly limit the conversion of CH4 to C2+ products. Herein, we demonstrate a metal-organic framework (MOF) crystal engineering strategy to synthesize a MOF-derived PdO/TiO2 nanocomposite for photocatalytic nonoxidative coupling of methane (NOCM), achieving high selectivity and activity in the conversion of CH4 to ethane (C2H6). Mechanistic investigations reveal that the spatially separated active sites for C-H bond cleavage and C-C coupling contribute to the efficient conversion of CH4 to C2H6. Specifically, the lattice oxygen captures the photogenerated holes, leading to the formation of oxygen radical anions (˙O-), which activate the C-H bond and generate ˙CH3 intermediates. PdO stabilizes ˙CH3 intermediates, effectively inhibiting the overoxidation of ˙CH3, and thereby promoting the C-C coupling process. This work opens a new avenue for the rational design of efficient MOF-derived photocatalysts for NOCM.

Implantable biological sensors can conduct continuous in-body monitoring, but they are confronted with a long-standing challenge: achieving self-powered operation and maintaining high molecular specificity in complex biological environments. Although near-infrared (NIR) light provides an ideal external energy source for its relatively deep tissue penetration and low phototoxicity, traditional near-infrared-based photoelectrochemical (PEC) biosensors often suffer from low charge separation efficiency due to photothermal losses. Here, we overturn this paradigm by converting photothermal loss into a productive thermoelectric driving force through a CRISPR-gated material assembly strategy. In this system, target-activated CRISPR-Cas12a acts as a molecular logic gate that programs the spatial assembly of MoSe2 nanoheaters onto a Bi2Te3 thermoelectric substrate. Under NIR irradiation, localized photothermal heating of MoSe2 establishes a temperature gradient across Bi2Te3, generating a Seebeck effect that drives directional charge separation and produces a robust photocurrent without external bias. This synergy between photothermal heating and topological-insulator-enhanced thermoelectric conversion enables attomolar detection of HPV-16 with excellent specificity and clinical agreement with qPCR. This work establishes a molecularly programmed energy-transduction framework in which CRISPR recognition is coupled to interfacial thermoelectric signal amplification, providing a design principle for future NIR-addressable self-powered biosensing systems.

The hydroxyethyl radical (center dot CH(CH3)OH)-mediated pathway, by avoiding the formation of aldehyde intermediates, constitutes a promising approach for the highly selective photocatalytic synthesis of benzimidazoles from ethanol and o-phenylenediamine. However, inefficient reactant adsorption and activation, as well as severe recombination of photogenerated charge carriers of traditional photocatalysts, impose a fundamental challenge for this reaction pathway. Herein, we construct an oxygen vacancy (VO)-rich Nb2O5 decorated with Pt nanoparticles (NPs), which exhibits the highest photocatalytic activity to date, with production rates of 4.0 mmol g(-1) h(-1) for 2-methylbenzimidazole and 10.2 mmol g(-1) h(-1) for H2, respectively. The synergistic interaction between VO and Pt NPs markedly promotes the migration and separation of photogenerated charge carriers. The electron-accumulating Pt NPs drive efficient H2 evolution through proton reduction, while the engineered VO sites enhance ethanol adsorption and selectively activate alpha-C-H bond cleavage to generate center dot CH(CH3)OH radicals, suppressing the accumulation of N-ethyl-2-methylbenzimidazole by-products inherent to conventional aldehyde-mediated reaction pathways, significantly facilitating the co-production of benzimidazoles and H-2. This work achieves directional pathway regulation via rational design of semiconductor defects and metal co-catalysts, establishing a radical-mediated strategy for efficient and selective green synthesis of N-heterocyclic compounds. (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Plastics are ubiquitous but pose severe environmental and health risks due to inadequate waste disposal, thereby necessitating the development of innovative and sustainable upcycling strategies to mitigate plastic pollution. Among chemical upcycling methods, photoredox-catalyzed plastic upcycling under mild conditions is particularly attractive, as it harnesses renewable solar energy to convert plastic waste into high-value chemicals. Notably, this process involves plastic oxidation coupled with various reduction half-reactions, where the rational selection of these reduction half-reactions influences plastic conversion efficiency and the co-production of high-value products. In this minireview, the reduction half-reactions involved in photocatalytic plastic oxidation are first categorized, and their fundamental principles and reaction pathways are outlined concurrently. Then, a summary of representative studies focusing on regulating photoredox half-reactions to drive the upgrading of plastic waste is presented, followed by a comprehensive outlook. This review is expected to provide valuable insights and directional guidance for advancing the upcycling of plastic waste through the rational regulation of photoredox half-reactions.

An effective cooperative photoredox system is developed for selective THIQ oxidation and efficient H 2 O 2 production over rGO-modified CdS catalysts (rGO–CdS).

Direct photocatalytic conversion of methanol into high-value multi-carbon chemicals through precisely controlled C - C coupling represents an extremely appealing but challenging goal. Herein, we demonstrate the efficient photoredox-driven dehydrocoupling of methanol into divergent synthesis of ethylene glycol and glycolaldehyde concomitantly with H2 production by structural regulation of atomically dispersed Ni species. We showcase distinctly different reaction pathway for divergent C - C coupling of methanol over two types of atomically dispersed Ni cocatalyst-decorated SiO quantum dots, namely those with single Ni atoms (Ni1-SiO/SiO2) and Ni clusters (Nin-CdS/SiO2). The Ni1-CdS/SiO2 generates ethylene glycol with 90% selectivity by a radical homo-coupling pathway, whereas the Nin-CdS/SiO2 achieves 96% selectivity towards glycolaldehyde by a radical addition-elimination pathway. This work not only offers a fascinating nonpetroleum route for the divergent C-C coupling synthesis of ethylene glycol and glycolaldehyde but also underscores the broad vista of modulating non-selective radicals toward selective transformation of methanol into multi-carbon products.

Cooperatively integrating CO2 reduction half-reaction with selective organic oxidation half-reaction presents an attractive opportunity to simultaneously utilize photogenerated holes and electrons to realize carbon neutrality and the production of value-added chemicals. Herein, we report the cooperative photoredox catalysis of tunable and efficient CO2 reduction to syngas paired with 4-methoxythiophenol (4-MTP) oxidation to bis(4methoxyphenyl) disulfide (4-MPD) over hybrid CdSe/CdS quantum dots (QDs). The strategy of constructing CdSe/CdS composites not only facilitates the efficiency of photoinduced carrier separation and transfer, improving the photoredox activity of two half-reactions, but also enhances CO2 activation, modulating the syngas CO/H2 ratio varying from 1:4-5:4. Mechanistic studies have revealed that 4-MTP is oxidized by holes located in CdS to generate hydrogen protons and sulfur-centered radicals, and then these radicals pair with each other to form 4-MPD with high selectivity, while the electrons in CdSe interact with protons and CO2 for syngas production. Furthermore, the feasibility of applying CdSe/CdS QDs to the cooperative photoredox catalysis of thiols with different substituents integrated with CO2 into corresponding disulfides and syngas has been demonstrated. This work envisages the development of QDs-based heterostructure catalysts for highly efficient photocatalytic co-production of syngas and value-added organic chemicals.

Nonthermal plasma (NTP) technology is emerging as a transformative engineering tool for the rational design and synthesis of advanced catalysts, addressing the critical limitations of conventional high‐temperature preparation methods. Operating under mild conditions, the unique nonequilibrium environment of NTP—rich in energetic electrons, ions, and reactive radicals—enables precise, multiscale control over catalyst properties. This allows for the creation of highly dispersed nanoparticles, tailored defect structures, and enhanced metal–support interactions that are often inaccessible via traditional thermal routes. This review provides a comprehensive overview of recent progress in applying NTP specifically as a synthesis and modification strategy to engineer high‐performance catalysts for the valorization of key greenhouse gases, namely CO 2 and CH 4 . We focus on how these NTP‐engineered catalysts exhibit superior activity, selectivity, and stability in critical reactions, including CO 2 hydrogenation, electrocatalytic and photocatalytic CO 2 reduction, and methane reforming. By elucidating the structure–performance relationships established through plasma‐based engineering, this review highlights the unique advantages of NTP in catalyst design and provides insights for the development of next‐generation catalysts for sustainable chemical production.

Converting CO2 into high-value hydrocarbons through solar-driven heterogeneous photocatalysis is deemed a salient technological avenue for achieving carbon neutrality, while confronting arduous challenges, which include the severe photogenerated charge carrier recombination and sluggish charge transfer kinetics. Herein, we propose an ingenious strategy of "synergistic dual-oxidative co-catalyst regulation" to customize the unidirectional cascade charge transfer pathway for enhanced photocatalytic CO2 reduction catalysis. By progressively assembling an oxygen-containing cobalt sulfide (CoSOH) and a layered double hydroxide (LDH) dual hole-trapping mediators onto the CdIn2S4 framework, we design a CdIn2S4/CoSOH/LDH ternary artificial photosystem, in which the CoSOH interlayer serves as a highway for charge transport relay, markedly accelerating the directional hole migration, while the CoAl-LDH acts as a terminal hole reservoir engendering a synergistic hole-relay mechanism. This dual-oxidative-cocatalyst-driven hole modulation strategy significantly enhances the charge separation/transfer and optimizes the surface reaction kinetics through the hole transport relay, considerably boosting the photocatalytic CO2 reduction activity. Our work affords a quintessential paradigm for strategically designing artificial photocatalysts with finely tuned spatial charge motion toward efficient solar-to-fuel conversion.

Glycolaldehyde (GA) possesses great potential to serve as the feedstock for the C 2 -based chemical industry and plays a vital role in the fabrication of pharmaceuticals and various chemicals. However, conventional GA synthesis methods suffer from harsh reaction conditions, low selectivity, and high purification costs. Herein, we for the first time demonstrate a new photoredox-catalyzed high-performance route toward dehydrogenative C─C coupling of methanol into GA paired with H 2 generation over Ni-decorated ZnIn 2 S 4 , presenting an essentially untapped photocatalytic tactic for selective GA synthesis. Specifically, GA is formed with the production rate of 30.0 mmol·g −1 ·h −1 and the selectivity of 94% and the optimal apparent quantum yield at λ = 360 nm reaches 22%, the highest value reported to date for selective photocatalytic methanol conversion to GA. Mechanistic studies reveal that the decoration of Ni facilitates interfacial charge separation and transfer and promotes the formation of key radical intermediates of •CH 2 OH and •OCH 3 for GA production. This work offers a conceptually new photocatalytic approach for the efficient and sustainable production of GA and enriches the content of methanol upcycling chemistry.

Atomically precise metal nanoclusters (NCs) demonstrate the unprecedented merits including unique atomic stacking pattern, quantum confinement effect, abundant active sites, and discrete energy band structure, filling the gap between single atoms and conventional metal nanocrystals. Integrating two metals into one nanocluster unit to craft bimetallic NCs (BNCs) significantly endow metal NCs with fascinating physicochemical properties, electronic structures, and metal-ligand interaction mechanisms through the bimetallic cooperative synergy. Nevertheless, there has still been a lack of comprehensive, insightful and timely overview on BNCs-based photoredox catalysis. Herein, this review recaps the category, synthetic strategies and characterization methods of a new generation of atomically precise BNCs, along with their recent exciting cutting-edge progress in diverse photoredox catalysis, including photocatalytic hydrogen production, CO2 reduction, selective organic transformation and environmental remediation. The charge transfer mechanisms and insight into structure-activity correlation in different redox catalysis reactions are elucidated. Eventually, future prospects and challenging tasks in this booming research field are discussed. The current review is expected to timely provide an emerging roadmap for customizing novel BNCs as a versatile photocatalyst platform toward solar energy conversion.

The incorporation of t-ZrO2 into alpha-Al2O3 matrix is a widely established method for enhancing the mechanical properties of ceramic materials, i.e., zicornia toughened alumina (ZTA). In this study, acetylacetonate zirconium and acetylacetonate yttrium were thoroughly mixed with alpha-Al2O3 powder and then calcined to achieve a uniform dispersion of organometallic-derived tetragonal zirconia polycrystal (TZP) particles in nano-size onto alpha-Al2O3, forming a composite powder. The TZP particle size increased from 8 to 39 nm with increasing calcination temperature from 600 to 1000 degrees C. The TZP nanoparticles coated alpha-Al2O3 powder was sintered by spark plasma sintering (SPS) to obtain ZTA ceramics. TZP is embedded in the face-centered cubic skeleton formed by alpha-Al2O3 and restricts grain growth to each other. The highest hardness and toughness, i.e., 18.81 GPa and 10.31 MPa m1/ 2, of the ZTA ceramics was achieved at 1400 degrees C by using the composite powder calcined at 600 degrees C.

Harnessing the power of photoredox catalysis for the selective C(sp3)-H activation and oxidation of alkyl aromatics represents a cutting-edge approach to transforming petroleum-derived feedstock into value-added C(sp3)-C(sp3) coupled chemicals. Herein, we delve into the photocatalytic process that involves the selective dehydrocoupling of ethylbenzene (EB) to access 2,3-diphenylbutane (DPB) alongside H2, employing three sulfur source-varied ZnIn2S4 (denoted as ZIS-x) catalysts. ZIS-TAA, with thioacetamide (TAA) as the sulfur source, exhibits exceptional photocatalytic efficiency for DPB and H2 production. The results show that the deficiency of charge carrier recombination centers in defect-poor ZIS-TAA is conducive to the separation of photogenerated charges. Additionally, the larger specific surface area and more surface functional groups provide abundant sites for reactant adsorption and activation, facilitating redox processes aided by an ideal band-edge structure. This work illustrates a simple and cost-effective paradigm for designing semiconductor-based photocatalysts with tailored surface properties to enhance the efficiency of target cooperative photoredox reactions.

2,3-Butanediol (2,3-BD) is a high-value chemical with wide applications in pharmaceuticals, polymers, and biofuels. Photocatalytic conversion of ethanol to 2,3-BD offers a promising route for sustainable chemical synthesis as it enhances the economic value of ethanol and reduces reliance on fossil fuels. In this study, we develop an efficient photocatalytic system for selective transformation of ethanol into 2,3-BD using Pt-modified Zn0.75Cd0.25S catalysts (Pt/Zn0.75Cd0.25S), demonstrating superior productivity and selectivity in neat ethanol compared to previous studies. The Pt nanoparticles on Zn0.75Cd0.25S significantly enhance the separation and transfer of charge carriers, thereby improving the photoredox catalytic activity. Moreover, the hydrogen bonding interactions between ethanol molecules and alpha-hydroxyethyl radical intermediates (center dot CH(OH)CH3) play a pivotal role in facilitating the C-C coupling reaction, optimizing the selectivity toward 2,3-BD. This work offers valuable insights for the rational design of Pt-modified semiconductor photocatalysts, facilitating the selective transformation of ethanol into value-added chemicals and clean H2 fuel.