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Solar-driven water splitting for hydrogen production is a vital approach to mitigating the energy crisis and achieving carbon neutrality and peak carbon emissions. Cd 0.8 Mn 0.2 S holds significant potential for photocatalytic hydrogen evolution but faces severe challenges due to photogenerated carrier recombination. To address this, we employed ultrasonic self-assembly to tightly couple Cu 2 WS 4 nanosheets with Cd 0.8 Mn 0.2 S nanoparticles, forming an S-scheme heterojunction to reduce carrier recombination rates. In this configuration, Cd 0.8 Mn 0.2 S acts as the electron acceptor, and Cu 2 WS 4 serves as the electron donor. The Cd 0.8 Mn 0.2 S/Cu 2 WS 4 structure creates a closely spaced interface, providing the shortest transfer distance for electron migration. The S-scheme heterojunction strategy effectively suppresses the recombination of photogenerated carriers, promoting vectorial separation. Under 10 W white light irradiation, the Cd 0.8 Mn 0.2 S/Cu 2 WS 4 composite photocatalyst exhibited remarkable hydrogen evolution activity, with a hydrogen production rate of 39.83 mmol g−1 h−1. This S-scheme heterojunction strategy lays the foundation for the structural design and large-scale application of high-activity visible-light photocatalysts. • Recombination of photogenerated carriers is inhibited. • Facilitated vector separation of photogenerated carriers. • In situ irradiated XPS validates the S-scheme heterojunction charge transfer mechanism. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Electron transfer is an important way to activate persulfate. Currently, the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself, which can lead to selective activation of persulfate or oxidation of the catalyst, respectively, and thus become a bottleneck restricting its application. In this work, Cu−doped FeVO4 (Cu−FVO) was prepared, and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate (PMS) activation. The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light. This system manifested a broad applicability to various organic contaminants even with complex matrix. Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO. Furthermore, Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS, through which photogenerated electrons achieved an efficient PMS activation. Meanwhile, holes were consumed by organic contaminants to avoid the oxidation of catalyst. These collectively enhanced the photocatalytic activity and stability of Cu−FVO, which also maintained high catalytic activity even after 20 cycling degradation reactions. [ABSTRACT FROM AUTHOR]

Here, we report CdS quantum dot (QD) gels, a three‐dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d‐HAT) photocatalyst for C−H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α‐amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C−H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C−H bonds are activated by the photoexcited CdS QD gel via a d‐HAT mechanism. This d‐HAT mechanism is supported by the linear correlation between the logarithm of the C−H bond activation rate constant and the C−H bond dissociation energy (BDE) with a Brønsted slope α=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C−H activation. [ABSTRACT FROM AUTHOR]

Supramolecular artificial light‐harvesting system with highly efficient host–guest energy transfer pathway provides an ideal platform for optimizing the photochemistry process. The consecutive photo‐induced electron transfer (conPET) process overcomes the energy limitation of visible‐light photocatalysis, but is often compromised by mismatching between the absorption of ground state dye and its radical, weakening the efficiency of photoredox reaction. By encapsulating a conPET photocatalyst rhodamine 6G into metal‐organic cage, the supramolecular approach was undertaken to tackle the intrinsic difficulty of matching the light absorption of photoexcitation between rhodamine 6G and its radical. The highly efficient Förster resonance energy transfer from the photoexcited cage to rhodamine 6G forced by host–guest encapsulation facilitates the conPET process for the single‐wavelength light‐driven activation of aryl halides by stabilizing and accelerating the production and accumulation of the rhodamine 6G radical intermediate. The tunable and flexible nature of the supramolecular host–guest complex renders the cage‐based encapsulation strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy. [ABSTRACT FROM AUTHOR]

Enhancement of the light-absorption response and utilization of the photogenerated carriers represent a robust strategy for the design of high-performance photocatalyst. In this work, grafting CoxP nanoclusters onto S-scheme heterojunction of W18O49/ZnIn2S4 (WO/ZIS-CoxP) with strong response to the ultraviolet–visible–near infrared ray (UV–vis–NIR) region has been achieved, which possesses efficient electron-transfer-channel, and boosts charge-separation and transport kinetics. The as-prepared WO/ZIS-CoxP yields an impressive solar-driven hydrogen production rate of 45 mmol·g−1·h−1. The increased photocatalytic performance is attributed to the synergistic effect of the composite catalyst: (1) The local surface plasmon resonance-induced "hot electron" injection of W18O49 significantly increases the electron density; (2) the engineered S-scheme directional electron transfer promotes charge separation and enhances the reducing capability of photoexcited electrons; and (3) CoxP as electron-trap site for accelerating surface proton reduction reaction. This work provides a platform to impart nonprecious co-catalyst for engineering S-scheme heterojunction, serving a class of efficient solar-driven photocatalyst towards hydrogen production. [ABSTRACT FROM AUTHOR]

Herein, a rational strategy is presented to reduce the energy barrier of singlet ground state to singlet excited state transitions, whilst simultaneously reducing energy losses in populating triplet excited states. The approach relies on constructing 3D space connected donor–acceptor systems in COFs. The 3D space connected D–A system in 8‐connected 3D COFs (denoted as COF‐1 and COF‐2) allows the efficient transfer of electrons, overcoming the traditional electron transport limitations of 2D COFs and significantly boosting the solar energy utilization efficiency under visible light irradiation. COF‐2, possessing an extended π‐conjugated structure relative to COF‐1, demonstrated high selectivity for the photocatalytic generation of H2O2 (6.93 mmol g−1 h−1) in natural seawater without the need for sacrificial reagents, exceeding the performance of most previously reported COF‐based photocatalysts. The 3D space connected D–A system reported in this work offers a new approach for optimizing electron and energy transfer in COF‐based photocatalysts for H2O2 production and other applications. [ABSTRACT FROM AUTHOR]

The need for carbon‐neutralization technologies has prompted significant interest in developing materials for CO2 reduction. Donor–acceptor (D–A) based flexible porous coordination polymers {[Zn(o‐phen)(ndc)].(guest)}n, (guest = anthracene = 1‐Ant, and pyrene = 1‐Pyr) are reported as photocatalysts for CO2RR, yielding higher order CH4 product. Electron‐rich anthracene (Ant) and pyrene (Pyr) guests are confined within nanopores, forming D–A charge transfer (CT) complexes with o‐phen ligand of the host. CT interaction enhances visible light absorption and modulates excitonic properties of the photocatalyst by electronic push‐pull effect (exciton binding energy 87 meV for 1‐Ant and 104 meV for 1‐Pyr). Electron donation capability varies from Pyr to Ant, affecting catalytic properties; 1‐Ant yields 1.24 mmolg−1 of CH4 (0.47 mmolg−1 for 1‐Pyr) with CO as minor product. A mixed‐metal multivariate PCP {[Zn0.55Co0.45(o‐phen)(ndc)].(Ant)}n, (1′‐Ant) prepared based on solid‐solution approach by substituting Zn(II) with redox‐active Co(II) enhances CH4 production (2.79 mmolg−1, ≈94% selectivity). D–A CT complex harvests visible light and channels electrons to Co(II) for CO2RR. In situ DRIFTS and theoretical studies elucidate Co(II) site's role in CO2 binding and stabilizing reaction intermediates. This work underscores guest‐modulated electron transfer in PCPs for tailoring catalytic properties by introducing a redox‐active metal in a multivariate approach. [ABSTRACT FROM AUTHOR]

The construction of heterojunctions is often considered an effective strategy for achieving visible light driven photocatalytic degradation of organic pollutants. In this work, defective g‐C3N4 ultrathin nanosheets were synthesized via alkaline etching method. Subsequently, a S‐scheme heterojunction was constructed between the contact interface of ZnO nanorods and alkaline C3N4 (aC3N4) to promote the electron transfer, resulting in a novel piezo‐photocatalyst (aC3N4/ZnO). The piezo‐photocatalytic performance of aC3N4/ZnO samples with different ratios was studied by adjusting the addition amount aC3N4. In addition, optimum 7 %‐aC3N4/ZnO samples exhibited the highest piezo‐photocatalytic degradation activity under light and ultrasonic irradiation with MB as the target pollutant, exhibiting the 99.89 % degradation rate and 65.68 % mineralization rate within 50 minutes. The capture experiments showed that 1O2,⋅O2− and ⋅OH were active substances in promoting the performance of piezo‐photocatalysis. The mechanism studies indicated that the enhanced piezo‐photocatalytic activity can be attributed to the synergistic effect of the piezoelectric properties of ZnO and the S‐scheme heterojunction formed at the aC3N4/ZnO interfaces, which provides power for the separation and transport of electron and hole. This work highlights the importance of carefully construction S‐scheme heterojunction and defective structures to precisely understand the catalytic properties, benefiting catalytic design and development. [ABSTRACT FROM AUTHOR]

Proton‐coupled electron transfer (PCET) imparts an energetic advantage over single electron transfer in activating inert substances. Natural PCET enzyme catalysis generally requires tripartite preorganization of proton relay, substrate‐bound active center, and redox mediator, making the processes efficient and precluding side reactions. Inspired by this, a heterogeneous photocatalytic PCET system was established to achieve higher PCET driving forces by modifying proton relays into anthraquinone‐based anionic coordination polymers. The proximally separated proton relays and photoredox‐mediating anthraquinone moiety allowed pre‐assembly of inert substrate between them, merging proton and electron into unsaturated bonds by photoreductive PCET, which enhanced reaction kinetics compared with the counter catalyst without proton relay. This photocatalytic PCET method was applied to a broad‐scoped reduction of aryl ketones, unsaturated carbonyls, and aromatic compounds. The distinctive regioselectivities for the reduction of isoquinoline derivatives were found to occur on the carbon‐ring sides. PCET‐generated radical intermediate of quinoline could be trapped by alkene for proton relay‐assisted Minisci addition, forming the pharmaceutical aza‐acenaphthene scaffold within one step. When using heteroatom(X)−H/C−H compounds as proton‐electron donors, this protocol could activate these inert bonds through photooxidative PCET to afford radicals and trap them by electron‐deficient unsaturated compounds, furnishing the direct X−H/C−H functionalization. [ABSTRACT FROM AUTHOR]

[Display omitted] The effectiveness of photocatalytic molecular oxygen (O 2) activation in pollutant removal relies on the targeted production of reactive oxygen species (ROS). Herein, we demonstrate the dual-pathway activation of O 2 on BiOCl through zirconium (Zr) loading. The incorporation of Zr onto the surface of BiOCl not only leads to an increased generation of oxygen vacancies (OV) but also fosters a coupling between the d electrons of Zr and OV, forming dual-active sites known as Zr-oxygen vacancies (Zr-OV). Generally, OV adsorbs O 2 and transfers one electron directly to form superoxide radicals (•O 2 –). Contrary to the conventional single-electron direct activation of O 2 to form •O 2 –, Zr-OV exhibits more flexible coordination and superior electron-donating capabilities. It facilitates O 2 conversion to peroxide radicals (O 2 2–) and enables the subsequent generation of •O 2 – from O 2 2–, significantly promotes the dechlorination and mineralization efficiency of chlorophenol under visible light. This study presents a straightforward strategy to precisely regulate ROS production by expanding pathways, shedding light on the critical role of managing ROS generation for effective pollutant purification. [ABSTRACT FROM AUTHOR]

The C10a‐acetoxylated tetrahydroazepino[1,2‐a]indole‐6,11‐diones are a class of tricyclic oxindoles that feature an α‐keto‐N,O‐acetal substructure, rendering them highly susceptible to SET reduction followed by fragmentation. In protic medium, they undergo a PCET‐assisted two‐step reduction including an interposed C−O bond cleavage that can be initiated photocatalytically as well as by cathodic reduction, and which generates nucleophilic ketyl radicals. In the presence of acrylonitrile and DIPEA as additional reactants, the photoinduced reaction unfolds as a tandem C−O bond reduction/ketyl radical conjugate addition, to furnish C10a‐reduced, C11‐cyanoethyl‐substituted tricyclic azepino‐[1,2‐a]indole derivatives with high stereoselectivity. [ABSTRACT FROM AUTHOR]

In this work, the successful synthesis of a Cu@g-C3N4/CeO2-like Z-scheme heterojunction through hydrothermal and photo-deposition methods represents high CO2 reduction activity with remarkable CO selectivity, as evidenced by the impressive CO yield of 33.8 μmol/g for Cu@g-C3N4/CeO2, which is over 10 times higher than that of g-C3N4 and CeO2 individually. The characterization and control experimental results indicate that the formation of heterojunctions and the introduction of Cu sites promote charge separation and the transfer of hot electrons, as well as the photothermal effect, which are the essential reasons for the improved CO2 reduction activity. Remarkably, Cu@g-C3N4/CeO2 still exhibits about 92% performance even after multiple cycles. In situ FTIR was utilized to confirm the production of COOH* at 1472 cm−1 and to elucidate the mechanism behind the high selectivity for CO production. The study's investigation into the wide-ranging applicability of the Cu@g-C3N4/CeO2-like Z-scheme heterojunction catalysts is noteworthy, and the exploration of potential reaction mechanisms for CO2 reduction adds valuable insights to the field of catalysis. [ABSTRACT FROM AUTHOR]

Based on the electron‐withdrawing effect of the Pt(bpy)Cl2 molecule, a simple post‐modification amide reaction was firstly used to graft it onto the surface of NH2‐MIL‐125, which performed as a highly efficient electron acceptor that induced the conversion of the photoinduced charge migration pathway from internal BDC→TiOx migration to external BDC→PtNx migration, significantly improving the efficiency of photoinduced electron transfer and separation. Furthermore, precisely regulating over the first coordination sphere of Pt single atoms was achieved using further post‐modification with additional bipyridine to investigate the effect of Pt−Nx coordination numbers on reaction activity. The as‐synthesized NML‐PtN2 exhibited superior photocatalytic hydrogen evolution activity of 7.608 mmol g−1 h−1, a remarkable improvement of 225 and 2.26 times compared to pristine NH2‐MIL‐125 and NML‐PtN4, respectively. In addition, the superior apparent quantum yield of 4.01 % (390 nm) and turnover frequency of 190.3 h−1 (0.78 wt % Pt SA; 129 times compared to Pt nanoparticles/NML) revealed the high solar utilization efficiency and hydrogen evolution activity of the material. And macroscopic color changes caused by the transition of carrier migration paths was first observed. It holds profound significance for the design of MOF‐Molecule catalysts with efficient charge carrier separation and precise regulation of single‐atom coordination sphere. [ABSTRACT FROM AUTHOR]

Dehydrogenation of unactivated alkanes to form versatile alkenes is an important but challenging task in synthetic chemistry. Enabled by a radical‐mediated formyl group migration, a novel visible light‐induced remote desaturation of aldehydes is developed, delivering a panel of trifluoromethylated δ,ϵ‐ or γ,δ‐unsaturated aldehydes in moderate to excellent yields with good functional group tolerance at room temperature. Mechanistic studies indicate a reaction pathway comprising the cascade trifluoromethylation of C−C double bonds, intramolecular addition to aldehydes, β‐fragmentation of alkoxy radicals, single electron transfer oxidation, and deprotonation. It provides a good complementary approach to the existing desaturation protocols. [ABSTRACT FROM AUTHOR]

Designing earth‐abundant metal complexes as efficient molecular photocatalysts for visible light‐driven CO2 reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine‐thiolate complex that functions both as a photosensitizer and catalyst for CO2 reduction. This single‐component bifunctional molecular photocatalyst efficiently reduced CO2 to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h−1 in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS)2 is indispensable step for photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Formamide (HCONH2) plays a pivotal role in the manufacture of a diverse array of chemicals, fertilizers, and pharmaceuticals. Photocatalysis holds great promise for green fabrication of carbon‐nitrogen (C−N) compounds owing to its environmental friendliness and mild redox capability. However, the selective formation of the C−N bond presents a significant challenge in the photocatalytic synthesis of C−N compounds. This work developed a photocatalytic radical coupling method for the formamide synthesis from co‐oxidation of ammonia (NH3) and methanol (CH3OH). An exceptional formamide yield rate of 5.47±0.03 mmol ⋅ gcat−1 ⋅ h−1 (911.87±5 mmol ⋅ gBi−1 ⋅ h−1) was achieved over atomically dispersed Bi sites (BiSAs) on TiO2. An accumulation of 45.68 mmol ⋅ gcat−1 (2.0 g ⋅ gcat−1) of formamide was achieved after long‐term illumination, representing the highest level of photocatalytic C−N compounds synthesis. The critical C−N coupling for formamide formation originated from the “σ–σ” interaction between electrophilic ⋅CH2OH with nucleophilic ⋅NH2 radical. The BiSAs sites facilitated the electron transfer between reactants and photocatalysts and enhanced the nucleophilic attack of ⋅NH2 radical on the ⋅CH2OH radical, thereby advancing the selective C−N bond formation. This work deepens the understanding of the C−N coupling mechanism and offers an intriguing photocatalytic approach for the efficient and sustainable production of C−N compounds. [ABSTRACT FROM AUTHOR]

The construction of secondary building units (SBUs) in versatile metal–organic frameworks (MOFs) represents a promising method for developing multi‐functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high‐nuclear transition‐metal‐based UiO‐architecture Co16‐MOF‐BDC with visible‐light‐absorbing capacity. Remarkably, the N3− molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible‐light‐absorbing chromophores via click reaction. The resulting Bodipy@Co16‐MOF‐BDC exhibits extremely high performance for oxidative coupling benzylamine (~100 % yield) via both energy and electron transfer processes, which is much superior to that of Co16‐MOF‐BDC (31.5 %) and Carboxyl @Co16‐MOF‐BDC (37.5 %). Systematic investigations reveal that the advantages of Bodipy@Co16‐MOF‐BDC in dual light‐absorbing channels, robust bonding between Bodipy/Co16 clusters and efficient electron‐hole separation can greatly boost photosynthesis. This work provides an ideal molecular platform for synergy between photosensitizing MOFs and chromophores by constructing high‐nuclear transition‐metal‐based SBUs with surface‐modifiable small molecules. [ABSTRACT FROM AUTHOR]

To address the constraints of CuInS2 in photocatalytic applications, ZnO was synthesized using the sol–gel technique, along with the in-situ hydrothermal method to acquire the ZnO/CuInS2 heterojunction photocatalyst. Comparisons with the pure CuInS2 monomer revealed that the fabricated composites demonstrated significant improvement in photocatalytic hydrogen production under simulated sunlight exposures. The optimal hydrogen production rate reached approximately 31-fold that of CuInS2 alone. The improved photocatalytic activity of ZnO/CuInS2 can be attributed to the successful formation of the heterojunction, which facilitates the effective transfer of electrons induced by light at the interface. Moreover, the composite photocatalyst significantly reduces electron–hole recombination resulting in efficient conversion of light energy to electrical energy. This study improves the performance of photocatalytic hydrogen production performance in CuInS2, providing a valuable reference for the development of photocatalytic hydrogen production catalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] Covalent organic frameworks (COFs) present bright prospects in visible light photocatalysis with abundant active sites and exceptional stability. Tailoring an established COF with photoactive group is a prudent strategy to extend visible light absorption toward broad photocatalysis. Here, a β-ketoenamine COF, TpBD-COF, constructed with 1,3,5-triformylphloroglucinol (Tp) and 4,4′-biphenyldiamine (BD), is tailored with azo to validate this strategy. The insertion of azo into BD affords 4,4′-azodianiline (Azo); TpAzo-COF is successfully constructed with Tp and Azo. Intriguingly, the insertion of azo enhances π-conjugation, thereby facilitating visible light absorption and intramolecular electron transfer. Moreover, TpAzo-COF, with an appropriate electronic structure and impressive specific surface area of 1855 m2 g−1, offers substantial active sites conducive to the reduction of oxygen (O 2) to superoxide. Compared with TpBD-COF, TpAzo-COF exhibits superior performance for blue light-driven oxidation of amines with O 2. Superoxide controls the selective formation of product imines. This work foreshadows the remarkable capacity of tailoring COFs with photoactive group toward broad visible light photocatalysis. [ABSTRACT FROM AUTHOR]

Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals. However, the lower photocatalytic efficiency due to the limited light trapping capacity, low electron transfer rate, and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application. Herein, we constructed a series of donor–acceptor (D–A) type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane (AB) hydrolysis. Under visible light irradiation at 20 °C, PtCo2@covalent organic framework (COF) showed the highest photocatalytic activity with a turnover frequency (TOF) of 486 min−1. Experiments and density functional theory (DFT) calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo2 nanoclusters. Specifically, the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework, and accelerate the photogenerated electron transfer from D–A type COF to PtCo2 nanocluster, which promotes the adsorption and activation of H2O and AB molecules and accelerates hydrogen release. Furthermore, PtCo2@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF. We believe that this work will provide a theoretical guide for the rational design of efficient D–A COF-based catalysts for photocatalysis. [ABSTRACT FROM AUTHOR]

Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research, however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming. In this work, we report an atomically precise Cu13 cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu4 tetrahedra. The Cu13H10(SR)3(PR' 3)7 (SR = 2,4-dichlorobenzenethiol, PR' 3 = P(4-FC6H4)3) cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H2 production. [ABSTRACT FROM AUTHOR]

[Display omitted] Mixed-dimensional van der Waals heterojunctions (MD-vdWhs), known for exceptional electron transfer and charge separation capabilities, remain underexplored in photocatalysis. In this study, we leveraged the synergistic effect of intermolecular π → π* and D-π-A dual channels to fabricate novel MD-vdWhs. Owing to the synergistic effect, it exhibits superior electron transfer and delocalization ability, thereby enhancing its photocatalytic performance. The Optimal photocatalyst can degrade 98.78 % of 20 mg/L tetracycline (TC) within 15 min. Additionally, we introduced a novel proof strategy for investigating the photoelectron transfer path, creatively demonstrating the synergistic dual channels effect, which can be attributed to the carbonyl density and light-excitation degree. Notably, even under low-power light sources, it achieved complete inactivation of Escherichia coli within just 7 mins, far surpassing current cutting-edge research. This theoretical framework holds promise for broader applications within related studies. [ABSTRACT FROM AUTHOR]

An innovative charge self-regulation strategy is proposed to construct a strongly interacting 2D/2D ReS 2 -MoS 2 in-plane hetero-cocatalyst, which collectively enables the activation of H 2 O molecules and subsequent H 2 evolution. [Display omitted] • A in-plane 2D/2D ReS 2 -MoS 2 hetero-catalyst was developed via molten salt methods. • H 2 -evolution rate of TiO 2 can be greatly improved by ReS 2 -MoS 2 hetero-cocatalyst. • The high activity of ReS 2 -MoS 2 was due to the formed Re(4−δ)+ and S(2−δ)− sites. • A charge self-regulation mechanism of ReS 2 -MoS 2 was proposed. The rationally designing and constructing atomic-level heterointerface of two-dimensional (2D) chalcogenides is highly desirable to overcome the sluggish H 2 O-activation process toward efficient solar-driven hydrogen evolution. Herein, a novel in-plane 2D/2D molybdenum disulfide-rhenium disulfide (ReS 2 -MoS 2) heterostructure is well-designed to induce the charge self-regulation of active site by forming electron-enriched Re(4−δ)+ and electron-deficient S(2−δ)− sites, thus collectively facilitating the activation of adsorbed H 2 O molecules and its subsequent H 2 evolution. Furthermore, the obtained in-plane heterogenous ReS 2 -MoS 2 nanosheet can powerfully transfer photoexcited electrons to inhibit photocarrier recombination as observed by advanced Kelvin probe measurement (KPFM), in-situ X-ray photoelectron spectroscopy (XPS) and femtosecond transient absorption spectroscopy (fs-TAS). As expected, the obtained ReS 2 -MoS 2 /TiO 2 photocatalyst achieves an outperformed H 2 -generation rate of 6878.3 μmol h−1 g−1 with visualizing H 2 bubbles in alkaline/neutral conditions. This work about in-plane 2D/2D heterostructure with strong free-electron interaction provides a promising strategy for designing novel and efficient catalysts for various applications. [ABSTRACT FROM AUTHOR]

Photocatalytic nitrogen reduction presents a promising technology for environmentally friendly ammonia synthesis under mild conditions. However, the performance of photocatalysts is often hindered by high charge carrier recombination and insufficient adsorption and activation of nitrogen molecules. A novel Bi 12 O 17 Cl 2 /BiOCOOH/Bi 2 MoO 6 heterojunction photocatalyst was successful synthesis through surface ion-exchange technique by potassium chloride. The introduction of Bi-rich Bi 12 O 17 Cl 2 on BiOCOOH/Bi 2 MoO 6 heterojunction not only improves electron transfer efficiency due to the dual type-II heterojunction effect but also facilitates on-site N 2 adsorption and activation for solar ammonia production by promoting oxygen vacancies. The high photocatalytic nitrogen fixation activity of the Bi 12 O 17 Cl 2 /BiOCOOH/Bi 2 MoO 6 was 107.78 μmol g−1 h−1 without any sacrificial agent. DFT calculations indicate that oxygen vacancies serve as the active site for adsorbed N 2 , the hydrogenation process preferentially forms on the distal N 2 atom with a lower activation energy about 0.6 eV. Therefore, the combination of oxygen vacancies and band engineering accelerates the production of ammonia. This endeavor holds the potential to unleash the capabilities of engineering for Bi-rich heterojunctions materials with oxygen vacancies, thereby achieving high-efficiency solar-driven N 2 -to-NH 3 conversion in aqueous environments. [Display omitted] • A novel Bi 12 O 17 Cl 2 /BiOCOOH/Bi 2 MoO 6 heterojunction photocatalyst through surface ion-exchange technique by potassium chloride. • The high photocatalytic nitrogen fixation activity of the Bi 12 O 17 Cl 2 /BiOCOOH/Bi 2 MoO 6 was 107.78 μmol g−1 h−1 without any sacrificial agent. • The built-in double type-II heterojunction promotes the on-site N 2 adsorption and activation of vacancy oxygen. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A visible light photocatalytic [3+2] cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein. By merging halogen atom transfer (XAT) and hydrogen atom transfer (HAT), alkyl/aryl iodides serve as a formal diradical precursor and add across C‐C triple bonds to deliver a number of functionalized cyclopentanes in moderate to high yields with exceptional regio‐ and diastereoselectivity. A reductive radical‐polar crossover mechanism, involving the cascade XAT, radical addition, 1,5‐HAT, polar effect‐promoted 5‐endo annulation, single electron transfer (SET) reduction, and protonation, may account for this unprecedented dehalogenative [3+2] cycloaddition. This work not only expands the repertoire of the traditional RATC methodology, but also provides a robust platform for the expedient assembly of cyclopentanes, a valuable structural motif in the realms of medicinal chemistry and material sciences. [ABSTRACT FROM AUTHOR]

[Display omitted] Photocatalytic technology is of great significance in environmental purification due to its eco-friendly and cost-effective operations. However, low charge-transfer efficiency restricts the photocatalytic activity of the catalyst. Herein, we report Cs 2 SnBr 6 /C 3 N 4 composite catalysts that exhibit a robust interfacial electron exchange thereby enhancing photocatalytic nitric oxide (NO) oxidation. A comprehensive study has demonstrated the S-scheme electron transfer mechanism. Benefiting from the interfacial internal electric field, the C-Br bond serves as a direct electron transfer channel, resulting in enhanced charge separation. Furthermore, the S-scheme heterojunction effectively traps high redox potential electrons and holes, leading to the production of abundant reactive oxygen radicals that enhance photocatalytic NO abatement. The NO removal rate of the Cs 2 SnBr 6 /C 3 N 4 heterogeneous system can reach 86.8 %, which is approximately 3-fold and 18-fold that of pristine C 3 N 4 and Cs 2 SnBr 6 , respectively. The comprehensive understanding of the electron transfer between heterojunction atomic interfaces will provide a novel perspective on efficient environmental photocatalysis. [ABSTRACT FROM AUTHOR]

Polycyclic indoles are prevailed in natural products, pharmaceuticals and biologically active compounds. Herein is described photo‐induced difluoromethylation‐cyclization of N‐alkene tethered indoles to synthesis of tetrahydropyrido[1,2‐a]indole using 5‐((difluoromethyl)sulfonyl)‐1‐phenyl‐1H‐tetrazole as a CF2H radical source. This photochemical reaction tolerates an array of functional groups like ester, cyano, ketone, halide, ether, aldehyde and heteocycles. Mechanistic experiments indicated that the difluoromethyl radical and the single electron transfer were involved. [ABSTRACT FROM AUTHOR]

TiO2 with the merits of non‐toxicity, high stability, strong redox capability, and low cost, has garnered considerable attention in the fields of renewable energy. However, the practical application is limited by the rapid recombination of photogenerated electron–hole pairs, posing a challenge to enhance electron utilization without compromising catalytic activity. Herein, S‐scheme TiO2@Co(OH)F‐Pt heterojunction through a simple hydrothermal and photo‐deposition method is constructed. The experimental tests and theoretical computation indicate that Co(OH)F possesses a smaller work function and a more negative conduction band (CB) position, significantly accelerating the separation of photogenerated charge carriers. Furthermore, the built‐in electric field, band bending between TiO2 and Co(OH)F, and the electron sink of Pt nanoparticles, facilitate the reduction of protons to hydrogen. The as‐prepared TiO2@Co(OH)F‐Pt exhibits high‐performance solar hydrogen evolution with an evolution rate of 1401 µmol h−1. The apparent quantum yield (AQY) is determined to be 22.8% at a single wavelength of 365 nm. After reacting 12 h for three cycles, no noticeable performance degradation occurs, showing good stability of the catalyst. This work provides a rational strategy for the design of heterojunction photocatalysts for driving the production of new energy and useful chemicals. [ABSTRACT FROM AUTHOR]

In semiconductor‐metal hybrid nanoparticles, excited charge carriers can be separated efficiently by transferring the electron to the metal, because the Fermi level is located within the bandgap of the semiconductor. Besides charge carrier separation, the catalytically active surface of the metal enables the use of these charge carriers for further reactions. Due to limited colloidal stability, the application of nanoparticles in solution is challenging. To circumvent these difficulties, the destabilization can be used to build monolithic 3D (non‐ordered) gel‐like structures with retained high surface area and an ensured diffusion within the network. Here, the resulting nanoparticle‐based hydrogels of CdSe/CdS/Pt nanoparticles show photocatalytic hydrogen production rates up to 58 (mmol(H2))/(g∙h). Due to the self‐supporting network structure, colloidal stability is unnecessary, and the applicability is improved. By simply mixing semiconductor and semiconductor–metal hybrid nanoparticles before gelation, the synthesis of the gels allows the reduction of the metal content, which further tunes the photocatalyst. [ABSTRACT FROM AUTHOR]

Photocatalytic nitrogen reduction represents a viable technology for green ammonia synthesis under mild conditions. However, the performance of the photocatalysts is typically limited by high charge carrier recombination and low adsorption and activation of nitrogen molecules. Herein, Bi/Bi2Sn2O7 (Bi/BSO) heterojunction nanocomposites are prepared via a one‐step hydrothermal method, where NaOH etching of oxygen vacancies in the Bi─O bonds of Bi2Sn2O7 (BSO) is exploited for the in situ formation of metallic Bi and hence Schottky junctions with the semiconducting BSO. This leads to a high separation rate of photogenerated charge carriers. Consequently, compared to the pure‐phase BSO, the Bi/BSO heterostructures exhibit markedly enhanced ammonia production, reaching an optimum rate of 284.5 µmol g−1 h−1, where the rectifying contact between the semiconducting BSO and metallic Bi facilitates directional BSO to Bi electron transfer, leading to enrichment of photogenerated electrons at the active sites of metallic Bi. First‐principles calculations confirm the alteration of active sites and the guided electron flow by the Schottky junctions and surface oxygen vacancies. Results from this study offer an effective paradigm of structural engineering in manipulating the photocatalytic activity of bismuth‐based pyrochlore materials toward nitrogen fixation to ammonia. [ABSTRACT FROM AUTHOR]

[Display omitted] • Interfacial complexation of Fe3+ and Bi 2 MoO 6 is established in the presence of PDS. • The complexation between Fe3+ and Bi 2 MoO 6 accelerates the Fe3+/Fe2+ cycle. • Efficient organic contaminants degradation is achieved by Bi 2 MoO 6 /Fe3+/PDS/Vis system. • The Fe3+/Fe2+ redox cycle is employed to promote the continuous activation of PDS. To address the observed decrease in efficiency during Fe2+-mediated persulfate (PDS) activation caused by slow electron transfer rates and challenges in cycling between Fe3+/Fe2+ states, we devised a strategy to establish interfacial complexation between Fe3+ and Bi 2 MoO 6 in the presence of PDS. The proposed approach facilitates more efficient capture of photogenerated electrons, thereby accelerating the rate-limiting reduction process of the Fe3+/Fe2+ cycle under visible light irradiation and promoting PDS activation. The Bi 2 MoO 6 /Fe3+/PDS/Vis system demonstrates complete degradation of organic pollutants, including Atrazine (ATZ), carbamazepine (CBZ), bisphenol A (BPA), and 2,4-dichlorophenol (DCP) at a concentration of 10 mg/L within a rapid reaction time of 30 min. Radical scavenging experiments and electron paramagnetic resonance spectra (EPR) confirm that the sulfate radical (•SO 4 −) is the dominant species responsible for organic contaminant degradation. The real-time conversion process between Fe3+ and Fe2+ was monitored by observing changes in iron species forms and concentrations within the reaction system. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy verify the formation of a complexation between Fe3+ and Bi 2 MoO 6 , facilitating anchoring of Fe3+ onto material surface. Based on these findings, we propose a reliable mechanism for the activation reaction. This work presents a promising heterogeneous PDS activation method based on Fe3+/Fe2+ cycle for water treatment. [ABSTRACT FROM AUTHOR]

A novel S-scheme ZnO-Zn 2 SnO 4 -based heterojunction with oxygen vacancies is in situ prepared. The synergistic effect of oxygen vacancies and S-scheme heterojunction not only generates rich active species but also activates small molecules, thereby greatly enhancing the deep oxidation efficiency of nitric oxide to nitrate under visible light irradiation. [Display omitted] The generation of hazardous intermediates during the process of photocatalytic nitric oxide (NO) oxidation presents a tough issue. Herein, a one-step microwave strategy was employed to introduce oxygen vacancies (OVs) into zinc oxide-zinc stannate (ZnO-Zn 2 SnO 4) heterojunction, resulting in an improvement in the photocatalytic efficiency for NO removal. The construction ZnO-Zn 2 SnO 4 heterojunction with the OVs (ZSO-3) owns a significant contribution towards highly efficient electron transfer efficiency (99.7%), which renders ZSO-3 to exert a deep oxidation of NO-to-nitrate (NO 3 −) rather than NO-to-nitrite (NO 2 −) or NO-to-nitrogen dioxide (NO 2). Based on the solid supports of experimental and simulated calculations, it can be found that OVs play an irreplaceable role in activating small molecules such as NO and O 2. Moreover, the enhanced adsorption capacity of small molecules, which guarantees the high yield of active radical due to the formation of S-scheme heterojunction. This work illuminates a novel viewpoint on one-step in-situ route to prepare Zn 2 SnO 4 -based heterojunction photocatalyst with deep oxidation ability of NO-to-NO 3 −. [ABSTRACT FROM AUTHOR]

Plant chloroplasts have a highly compartmentalized interior, essential for executing photocatalytic functions. However, the construction of a photocatalytic reaction compartment similar to chloroplasts in inorganic–biological hybrid systems (IBS) has not been reported. Drawing inspiration from the compartmentalized chloroplast and the phenomenon of liquid–liquid phase separation, herein, a new strategy is first developed for constructing a photocatalytic subcellular hybrid system through liquid–liquid phase separation technology in living cells. Photosensitizers and in vivo expressed hydrogenases are designed to coassemble within the cell to create subcellular compartments for synergetic photocatalysis. This compartmentalization facilitates efficient electron transfer and light energy utilization, resulting in highly effective H2 production. The subcellular compartments hybrid system (HM/IBSCS) exhibits a nearly 87‐fold increase in H2 production compared to the bare bacteria/hybrid system. Furthermore, the intracellular compartments of the photocatalytic reactor enhance the system's stability obviously, with the bacteria maintaining approximately 81% of their H2 production activity even after undergoing five cycles of photocatalytic hydrogen production. The research brings forward visionary prospects for the field of semi‐artificial photosynthesis, offering new possibilities for advancements in areas such as renewable energy, biomanufacturing, and genetic engineering. [ABSTRACT FROM AUTHOR]

The electronic structure and photophysical properties of several acrylaldehyde‐bridged deazaflavin derivatives (cFLs) were investigated theoretically. The impact of acrylaldehyde bridging on photophysical properties of deazaflavin (cFL) is strongly site‐dependent. Specifically, the change of adiabatic energy of electronic transitions(ΔEad) and vibronic coupling promote fluorescent emission to be comparable to internal conversion of cFL and cFL4 (both C5−C6 and C9−N10 bridged, but C9−N10 bridged by propene), turning them eligible as fluorescent sensors. As El‐Sayed's rule is satisfied in cFL1(C5−C6 bridged), cFL2(C9−N10 bridged) and cFL3(both C5−C6 and C9−N10 bridged), intersystem crossing from first singlet excited state to triplet excited states (Tn) become dominant and the evolution of excited cFLs from T1 appears vital. The rate constants of photophysical processes indicate these cFLs are of dominantly high steady state T1 concentration and are potential triplet sensitizers. We expect the findings would pave the way for rational design of novel cFLs with extraordinary photophysical properties. [ABSTRACT FROM AUTHOR]

Graphdiyne (GDY) is flourishing in the field of photocatalysis due to its high conductivity and enhancement of electron transfer. Electron transport can be expedited when GDY is used as a catalytic support. Herein, a GDY/NiCo 2 O 4 composite photocatalyst was constructed in situ using organic compounds and bimetallic oxides. Furthermore, Cu 2 O was introduced into the GDY/NiCo 2 O 4 interface through interfacial engineering, which effectively enhanced the activity of the catalyst. Electrochemistry and fluorescence spectroscopy demonstrated that the load of Cu 2 O can reduce the electron transfer resistance and decrease the photogenerated carrier recombination carrier rate. The formation of S-scheme heterojunction formed by Cu 2 O, GDY and NiCo 2 O 4 can accelerate the electron transfer through band bending and internal electric field and improve the reducing activity of the catalyst. The outcomes of this work demonstrate the potential applications of Cu 2 O and GDY in photocatalysis and provide insights into the construction of high-performance photocatalysts. Benefiting from the double S-scheme heterojunction formed by Cu 2 O, GDY, and NiCo 2 O 4 and the excellent electrical conductivity of graphdiyne, the synthesized composite photocatalysts effectively inhibit the photogenerated charge recombination and enhance the hydrogen production performance. [Display omitted] • Preparation of graphdiyne by the mechanic ball milling. • Excellent electrical conductivity of graphdiyne facilitates the charge transfer. • The double S-scheme can effectively inhibit photogenerated carrier recombination. • The addition of Cu 2 O greatly improves the charge transfer capability of the system. [ABSTRACT FROM AUTHOR]

Synthesizing fine chemicals and valuable pharmaceutical intermediates through selective catalytic oxidation of alcohols is indispensable and crucial. However, the conventional methods of alcohol oxidation have inevitable drawbacks, including harsh reaction conditions and environmental pollution. Thus, it is imperative to develop efficient catalytic oxidation systems for alcohols. Herein, we successfully synthesized a 15 wt %PI‐TiO2 composite by a one‐step solid‐state heating polymerization technique. This catalyst exhibits excellent responsiveness to visible light and demonstrates remarkable catalytic activity. Furthermore, TEMPO was introduced as a cocatalyst to construct a PI‐TiO2/TEMPO/O2 system for the catalytic oxidation of alcohols. In comparison to the individual effects of PI or TiO2, this system showcases improved catalytic activity and broader substrate applicability. As a result, the conversion efficiency of benzyl alcohol increases by 3.44 times and 2.26 times, respectively. This research not only introduces a novel approach for preparing visible light‐active PI‐TiO2 catalysts but also indicates the significance of establishing an efficient electron transfer process in alcohol catalytic oxidation. [ABSTRACT FROM AUTHOR]

Van der Waals (vdW) heterojunctions enhance photocatalyst efficiency but face electron transfer challenges at component interfaces due to large spacing and potential barriers. We introduce a novel wet chemistry approach to enhance the efficiency of photocatalysts by creating a functionalized graphene-modulated Z-scheme vdW heterojunction (xZnPc/yG-WO 3) to eliminate interfacial potential differences, enabling better electron transfer for improved photocatalytic reactions and molecular dispersion. [Display omitted] The construction of van der Waals (vdW) heterojunctions is a key approach for efficient and stable photocatalysts, attracting marvellous attention due to their capacity to enhance interfacial charge separation/transfer and offer reactive sites. However, when a vdW heterojunction is made through an ex-situ assembly, electron transmission faces notable obstacles at the components interface due to the substantial spacing and potential barrier. Herein, we present a novel strategy to address this challenge via wet chemistry by synthesizing a functionalized graphene-modulated Z-scheme vdW heterojunction of zinc phthalocyanine/tungsten trioxide (xZnPc/yG-WO 3). The functionalized G-modulation forms an electron "bridge" across the ZnPc/WO 3 interface to improve electron transfer, get rid of barriers, and ultimately facilitating the optimal transfer of excited photoelectrons from WO 3 to ZnPc. The Zn2+ in ZnPc picks up these excited photoelectrons, turning CO 2 into CO/CH 4 (42/22 μmol.g−1.h−1) to deliver 17-times better efficiency than pure WO 3. Therefore, the introduction of a molecular "bridge" as a means to establish an electron transfer conduit represents an innovative approach to fabricate efficient photocatalysts designed for the conversion of CO 2 into valued yields. [ABSTRACT FROM AUTHOR]

Single‐metal atomic sites and vacancies can accelerate the transfer of photogenerated electrons and enhance photocatalytic performance in photocatalysis. In this study, a series of nickel hydroxide nanoboards (Ni(OH)x NBs) with different loadings of single‐atomic Ru sites (w‐SA‐Ru/Ni(OH)x) were synthesized via a photoreduction strategy. In such catalysts, single‐atomic Ru sites are anchored to the vacancies surrounding the pits. Notably, the SA‐Ru/Ni(OH)x with 0.60 wt % Ru loading (0.60‐SA‐Ru/Ni(OH)x) exhibits the highest catalytic performance (27.6 mmol g−1 h−1) during the photocatalytic reduction of CO2 (CO2RR). Either superfluous (0.64 wt %, 18.9 mmol g−1 h−1; 3.35 wt %, 9.4 mmol−1 h−1) or scarce (0.06 wt %, 15.8 mmol g−1 h−1; 0.29 wt %, 21.95 mmol g−1 h−1; 0.58 wt %, 23.4 mmol g−1 h−1) of Ru sites have negative effect on its catalytic properties. Density functional theory (DFT) calculations combined with experimental results revealed that CO2 can be adsorbed in the pits; single‐atomic Ru sites can help with the conversion of as‐adsorbed CO2 and lower the energy of *COOH formation accelerating the reaction; the excessive single‐atomic Ru sites occupy vacancies that retard the completion of CO2RR. [ABSTRACT FROM AUTHOR]

We report on a protocol for the hydroxyalkenylation of alkenes using an acridinium photoredox catalyst in combination with 1,2‐bis(phenylsulfonyl)ethylene and water. Using the protocol, alkenes could be converted into the corresponding 1‐phenylsulfonyl‐4‐hydroxyalkenes in good yields. The hydroxyalkenylation involves the nucleophilic hydroxylation of alkene‐derived radical cations to give β‐hydroxyalkyl radicals, which then undergo a radical addition/β‐elimination sequence. The catalytic cycle is likely sustained by electron transfer from the acridine radical to the benzenesulfonyl radical, which is formed via a radical addition/elimination sequence. [ABSTRACT FROM AUTHOR]

A facile solvent-free solid-state method was adapted to synthesize the spherical-shaped Bi2WO6 engraved on phenyl-doped g-C3N4 nanosheet, i.e., Bi2WO6/Ph-gC3N4 (or BPCN) composites with varying weights of Bi2WO6. Several spectral analyses were used to characterize all the synthesized nanomaterials. The synthesized photocatalyst showed good absorption under visible light as confirmed by UV–visible DRS analysis. Morphological analyses like SEM and TEM determine the successful fabrication of binary heterocomposite. Further, the elements available in the fabricated binary nanocomposite were confirmed by XPS. The photocatalyst was used for the aerobic photocatalytic degradation of a few colorless pollutants like bisphenol A (BPA, 30 mg L−1), a microplastic constituent, and tetracycline (TC, 40 mg L−1), an antibiotic derivative to achieve the impressive results. The less intense PL signal obtained for the 20BPCN heterocomposite reveals the remarkable enhancement in e−-h+ pair separation and recombination rate. The quenching study, alkaline terephthalic acid photoluminescence test (TA-PL), and NBT phototransformation study explain the formation of reactive species involved in the decomposition process. An oral cancer cell line (A-254) was tested for the anticancer activity analysis of the 20BPCN photocatalyst. Based on the obtained results, a Z-scheme electron transfer mechanism has been proposed for the photodegradation of model compounds. [ABSTRACT FROM AUTHOR]

Herein, we report a photocatalytic method for the synthesis of 2‐quinolones under mild conditions by employing α‐diazo acetamide as substrates. The use of Eosin Y as a photocatalyst allows an economical and environmentally benign synthetic method. The process involves the generation of radicals from diazo compounds promoted by a visible‐light‐induced proton‐coupled electron transfer (PCET) mechanism. The method demonstrates a broad substrate scope to provide various aryl‐ and alkyl‐substituted 2‐quinolones. To support the proposed mechanism, a series of mechanistic experiments were conducted. [ABSTRACT FROM AUTHOR]

Ru‐catalyzed directing group assisted C−H functionalization of arenes remains one of the powerful tools for site selective organic synthesis. Previous thermos versions normally require high temperature, rendering low functional group tolerance. With the emergence of the photoredox chemistry, visible light mediated mild Ru‐catalyzed directed C−H activation, especially using [RuCl2(p‐cymene)]2 as catalyst, have recently been investigated. Meta, ortho, and para selectivity have been achieved owing to the different activation mode of ruthenium complex. Inner‐sphere electron transfer and outer‐sphere electron transfer redox processes were attributed to different reaction pathway. In this review, we will provide an overview on recent achievements in visible light mediated Ru‐catalyzed directed C−H activation of arenes. [ABSTRACT FROM AUTHOR]

The development of photocatalysts with continuous electron extraction and rapid proton transfer could kinetically accelerate the artificial photosynthesis, but remains a challenge. Herein, we report the topology‐guided synthesis of a high‐crystalline triazine covalent organic framework (COF) decorated by uniformly distributed polar oxygen functional groups (sulfonic group or carboxyl) as the strong electron/proton extractor for efficient photocatalytic H2O2 production. It was found that the polarity‐based proton transfer as well as electron enrichment in as‐obtained COFs played a crucial role in improving the H2O2 photosynthesis efficiency (i.e. with an activity order of sulfonic acid‐ (SO3H‐COF)>carboxyl‐ (COOH‐COF)>hydrogen‐ (H‐COF) functionalized COFs). The strong polar sulfonic acid group in the high‐crystalline SO3H‐COF triggered a well‐oriented built‐in electric field and more hydrophilic surface, which serves as an efficient carrier extractor enabling a continuous transportation of the photogenerated electrons and interfacial proton to the active sites (i.e. C atoms linked to −SO3H group). As‐accelerated proton‐coupled electron transfer (PCET), together with the stabilized O2 adsorption finally leads to the highest H2O2 production rate of 4971 μmol g−1 h−1 under visible light irradiation. Meanwhile, a quantum yield of 15 % at 400 nm is obtained, superior to most reported COF‐based photocatalysts. [ABSTRACT FROM AUTHOR]

The development of novel materials for highly efficient and selective photocatalysis is crucial for their practical applications. Herein, we employ the host‐guest chemistry of porphyrin‐based metallacages to regulate the generation of reactive oxygen species and further use them for the selective photocatalytic oxidation of benzyl alcohols. Upon irradiation, the sole metallacage (6) can generate singlet oxygen (1O2) effectively via excited energy transfer, while its complex with C70 (6⊃C70) opens a pathway for electron transfer to promote the formation of superoxide anion (O2⋅−), producing both 1O2 and O2⋅−. The addition of 4,4′‐bipyridine (BPY) to complex 6⊃C70 forms a more stable complex (6⊃BPY) via the coordination of the Zn‐porphyrin faces of 6 and BPY, which drives fullerenes out of the cavities and restores the ability of 1O2 generation. Therefore, benzyl alcohols are oxidized into benzyl aldehydes upon irradiation in the presence of 6 or 6⊃BPY, while they are oxidized into benzoic acids when 6⊃C70 is employed as the photosensitizing agent. This study demonstrates a highly efficient strategy that utilizes the host‐guest chemistry of metallacages to regulate the generation of reactive oxygen species for selective photooxidation reactions, which could promote the utilization of metallacages and their related host‐guest complexes for photocatalytic applications. [ABSTRACT FROM AUTHOR]

It has been proven that constructing heterojunction can efficiently improve the activity of single component photocatalyst. Herein, an S-scheme CuCo 2 S 4 /g-C 3 N 4 heterojunction was synthesized via a physical mixing strategy with a solvent evaporation process. Photocatalytic performance of the binary composites was obviously improved compared to CuCo 2 S 4 (CCS) or g-C 3 N 4 (CN). Under the irradiation of 300 W Xe lamp, the H 2 generation rate of CCS/CN-20 reaches up to 2487 μmol g−1 h−1 in 20 vol % triethanolamine (TEOA), which is approximately 22.4- and 18-fold as those of CCS and CN, respectively. Furthermore, the H 2 production of CCS/CN-20 still reaches 89 % of initial amount after 3 cycles. The significantly enhanced performance is because the unique photogenerated carrier transfer channel established between the two catalysts, which helps to generate more active sites, reduce the H 2 evolution over-potential and improve the light absorption. A combination of density functional theory calculations and energy band structure analysis confirms that the electrons transfer between CCS and CN follows S-scheme pathway, which not only facilitates the spatial separation of photoexcited charges but also improves oxidation and reduction capacity. This work provides momentous reference and inspiration for the construction of highly active g-C 3 N 4 -based photocatalyst. [Display omitted] • CuCo 2 S 4 /g-C 3 N 4 composite is fabricated via physical mixing strategy and solvent evaporation methods. • CuCo 2 S 4 /g-C 3 N 4 heterojunction exhibits a significant enhancement in H 2 evolution rate compared to g-C 3 N 4. • The charge carrier transfer follows the S-scheme route between CuCo 2 S 4 and g-C 3 N 4. [ABSTRACT FROM AUTHOR]

Conductive metal–organic frameworks (c‐MOFs) have aroused extensive attention due to their excellent properties by integrating the features of both conductive and porous crystalline materials. Recent investigations in miniaturization of c‐MOFs into nanostructured conductive MOFs (nc‐MOFs) endow them with additional advantages such as reduced diffusion distance, accelerated mass/electron transfer, enhanced active site exposure, and accessibility, further widening their applications with reinforced performances compared to the conventional bulk counterparts. Herein, a timely review on the latest achievements in the field of nc‐MOFs is provided. First, we systematically introduce the synthetic strategies for producing nc‐MOFs with controllable morphologies and compositions. Second, the enhanced performance of nc‐MOFs in electrocatalysis, supercapacitors, batteries, sensors, and photocatalysis is highlighted. Finally, a discussion on the challenges and opportunities of the synthesis and applications of nc‐MOFs is presented. It is expected that this review will shed light on the future development of nc‐MOFs with promising application potential. [ABSTRACT FROM AUTHOR]

Graphitic carbon nitride semiconductors are inexpensive and reusable photocatalysts, which are actively studied in organic synthesis. Successful design of photocatalytic reactions is based on the next considerations. i) Thermodynamic feasibility of photoinduced processes, which involve transfer of electrons or electron‐proton couples. ii) Redox activity of reagents. iii) Reactivity of the open‐shell intermediates generated from the reagents. Herein, we summarize current understanding of how local chemical structure of graphitic carbon nitrides and their redox potentials are used to design photocatalytic reactions. This work intends to serve as a guideline for materials scientists, who are willing to apply their carbon nitride semiconductors in reactions involving organic substrates, and for organic chemists, who are interested to dive into heterogeneous carbon nitride photocatalysis. [ABSTRACT FROM AUTHOR]

Anchoring of single-atom Pt2+ and Pt0 on the surface of Sb 2 S 3 NRs highly benefits to the formation of metal (Pt)-semiconductor (Sb 2 S 3) electric interaction, which synergistically improves the broadband light harvesting and promotes the Sb 2 S 3 -to-Pt electron transfer following inhibited photoexciton recombination kinetics and enhanced H proton adsorption capacity, resulting higher and more durable photoactivity for H 2 O-to-H 2 conversion. [Display omitted] • Single atomic Pt2+/Pt0 active sites were successfully anchored on the Sb 2 S 3 nanorods. • The metal (Pt)-semiconductor (Sb 2 S 3) electric interaction was formed. • The optimal composite catalyst possesses enhanced H proton adsorption capacity. • Higher and more durable photoactivity for H 2 O-to-H 2 conversion were achieved. • The mechanism of multisite cocatalysis for photoactivity improvement was elucidated. Single atomic metal (SAM) cocatalysis is a potential strategy to improve the performance of photocatalytic materials. However, the cocatalytic mechanism of SAM sites in different valence states is rarely reported. Herein, single atomic Pt2+/Pt0 active sites were anchored on Sb 2 S 3 nanorods to synergistically improve the photoactivity for hydrogen production under simulated sunlight. Experimental results and density functional theory calculations indicated that the coexistence of single atomic Pt2+/Pt0 sites synergistically improves the broadband light harvesting and promotes the Sb 2 S 3 -to-Pt electron transfer following inhibited photoexciton recombination kinetics and enhanced H proton adsorption capacity, resulting higher and more durable photoactivity for hydrogen production. Therefore, the optimal Sb 2 S 3 -Pt 0.9‰ composite catalyst achieved remarkably enhanced hydrogen evolution rate of 1.37 mmol∙g−1∙h−1 (about 105-fold greater of that of Sb 2 S 3 NRs) under faintly alkaline condition, and about 5.41 % of apparent quantum yield (AQY 700 nm) was achieved, which shows obvious superiority in hydrogen production by contrasting with the reported Sb 2 S 3 -based photocatalysts and conventional semiconductor photocatalytic materials modified with noble metals. This study elucidate a well-defined mechanism of multisite cocatalysis for photoactivity improvement. [ABSTRACT FROM AUTHOR]

Modifying redox potential of substrates and intermediates to balance pairs of redox steps are important stages for multistep photosynthesis but faced marked challenges. Through co‐clathration of iridium photosensitizer and imine substrate within one packet of a metal‐organic capsule to shift the redox potentials of substrate, herein, we reported a multiphoton enzymatic strategy for the generation of heterocycles by intramolecular C−X hydrogen evolution cross‐couplings. The cage facilitated a pre‐equilibrium substrate‐involving clathrate that cathodic shifts the oxidation potential of the substrate‐dye‐host ternary complex and configuration inversion of substrate via spatial constraints in the confined space. The new two photon excitation strategy enabled the precise control of the multistep electron transfer between each pair (photosensitizer, substrate and the capsule), endowing the catalytic system proceeding smoothly with an enzymatic fashion. Three kinds of 2‐subsituted (−OH, −NH2, and −SH) imines and N‐aryl enamines all give the corresponding cyclization products efficiently under visible light irradiation, demonstrating the promising of the microenvironment driven thermodynamic activation in the host‐dye‐substrate ternary for synergistic combination of multistep photocatalytic transformations. [ABSTRACT FROM AUTHOR]

Finely modulated light-induced charge separation and transfer is a central challenge to achieve efficient photocatalysis. Although progress has been made in this field, most of the previous research works focused on the separation or migration of photogenerated carriers but did not build a bridge between the two. How to realize the strong driving and precise migration of carriers has become the focus of our work. We report an ingeniously designed ternary heterojunction. Taking NiFe-MOF as the "parent material", the FeP 4 /Ni x P y heterojunction is derived in situ while maintaining the frame structure through gas-solid reaction, and finally the Z-type electron transfer is realized. With Cu 3 P anchoring spindle matrix, an electron transport tunnel is opened up in Cu 3 P/FeP 4 /Ni x P y ternary heterojunction under the action of p-n heterojunction built-in electric field driving and accurate energy band matching. The strong driving force of the built-in electric field provides an inexhaustible power for the transmission of electrons, and the fine series of electron transmission channels realizes the precise transmission of electrons. The above fine design makes the perfect fit between the built-in electric field and the electron transfer channel, which not only effectively improves the embarrassing situation of insufficient electron driving force of hydrogen evolution reaction in the previous research, but also makes up for the weakening of semiconductor reduction ability caused by the construction of traditional p-n heterostructures. This research work provides a new idea for the construction of multiple heterostructures and the design of fine interface engineering in the future. [ABSTRACT FROM AUTHOR]