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The use of metal-free carbon nitride and light to drive catalytic transformations constitutes a sustainable strategy for organic synthesis. At the moment, enhancing the intrinsic activity of CN catalysts by tuning the interfacial coupling between catalyst and substrate remains challenging. Herein, we demonstrate that urea-derived carbon nitride catalysts with the abundant −NH 2 groups and the relative positive charged surface could effectively complex with the deprotonated anionic intermediate to improve the adsorption of organic reactants on the catalyst surface. The decreased oxidation potential and upshift in its highest occupied molecular orbital position make the electron abstraction kinetics by the catalyst more energetically favorable. The prepared catalyst is thus utilized for the photocatalytic cyclization of nitrogen-centered radicals for the synthesis of diverse pharmaceutical-related compounds (33 examples) with high activity and reusability, which shows competent performance to the homogeneous catalysts. Carbon nitride catalysts with positively charged surfaces and abundant −NH2 are found to be effective photocatalysts for dihydropyrazole synthesis. A surface-mediated mechanism where deprotonated intermediates interact with the surface is proposed.

Unraveling how reactive facets promote photocatalysis at the molecular level remains a grand challenge, while identification of the reactive facets can provide guidelines for designing highly efficient photocatalysts and unravelling the microscopic mechanisms behind them. Recently, a series of polytriazine imides (PTIs) was reported with highly crystalline structures; all had a relatively low photocatalytic activity for overall water splitting. Here, high-angle annular dark-field scanning transmission electron microscopy, energy dispersive spectroscopy mapping, and aberration-corrected integrated differential phase contrast imaging were used to study PTI/Li + Cl − single crystals before and after in situ photodeposition of co-catalysts, showing that the prismatic {10 1 ¯ 0} planes are more photocatalytically reactive than the basal {0001} planes. Theoretical calculations confirmed that the electrons are energetically favourable to transfer toward the {10 1 ¯ 0} planes. Upon this discovery, PTI/Li + Cl − crystals with different aspect ratios were prepared, and the overall water splitting performance followed a linear correlation with the relative surface areas of the {10 1 ¯ 0} and {0001} planes. Our controlling of the reactive facets directly instructs the development of highly efficient polymer photocatalysts for overall water splitting. Unlike with inorganic photocatalysts, the facet-dependent reactivity of conjugated polymers remains elusive. Now, the authors provide molecular-level insights on the reactive facets of crystalline poly(triazine imide) intercalated with LiCl and achieve a remarkable improvement in its overall photocatalytic water splitting activity.

Construction of internal electric fields (IEFs) is crucial to realize efficient charge separation for charge-induced redox reactions, such as water splitting and CO 2 reduction. However, a quantitative understanding of the charge transfer dynamics modulated by IEFs remains elusive. Here, electron microscopy study unveils that the non-equilibrium photo-excited electrons are collectively steered by two contiguous IEFs within binary (001)/(200) facet junctions of BiOBr platelets, and they exhibit characteristic Gaussian distribution profiles on reduction facets by using metal co-catalysts as probes. An analytical model justifies the Gaussian curve and allows us to measure the diffusion length and drift distance of electrons. The charge separation efficiency, as well as photocatalytic performances, are maximized when the platelet size is about twice the drift distance, either by tailoring particle dimensions or tuning IEF-dependent drift distances. The work offers great flexibility for precisely constructing high-performance particulate photocatalysts by understanding charge transfer dynamics. While internal electric fields alter charge-separation dynamics in solar-to-chemical conversions, a greater understanding of such processes is necessary. Here, authors analyze charge transfer dynamics modulated by built-in electric fields and identify carrier drift distances as a critical parameter.

Natural photosynthesis occurs in the thylakoid membrane where functional proteins and electron carriers are precisely arranged to efficiently convert sunlight into a chemical potential between the two membrane sides, via charge separation and electron transport chains, for use in oxygen generation and CO 2 fixation. These light-harvesting complexes and cofactors have been actively mimicked using dyes, semiconductors and catalytic nanoparticles. However, the photosynthetic scaffold that optimizes both the capture and distribution of light and separates both the oxidative and reductive species has been mimicked much less often, especially using polymer substances. Here we report the synthesis of hollow nanospheres sized in the optical range and made of a robust semiconductor, melon or carbon-nitride polymer. These hollow nanospheres are shown to function as both light-harvesting antennae and nanostructured scaffolds that improve photoredox catalysis, which was determined to have a 7.5% apparent quantum yield via a hydrogen-generation assay. Photosynthesis occurs at the thylakoid membrane, which acts as a scaffold, precisely arranging functional proteins and electron carriers. Sun et al. synthesize hollow photosynthetic nanospheres that function as light-harvesting antennae and structured scaffolds that improve photoredox catalysis.

Construction of organic semiconducting materials with in-plane π-conjugated structures and robustness through carbon-carbon bond linkages, alternatively as organic graphene analogs, is extremely desired for powerfully optoelectrical conversion. However, the poor reversibility for sp 2 carbon bond forming reactions makes them unavailable for building high crystalline well-defined organic structures through a self-healing process, such as covalent organic frameworks (COFs). Here we report a scalable solution-processing approach to synthesize a family of two-dimensional (2D) COFs with trans -disubstituted C = C linkages via condensation reaction at arylmethyl carbon atoms on the basis of 3,5-dicyano-2,4,6-trimethylpyridine and linear/trigonal aldehyde (i.e., 4,4″-diformyl- p -terphenyl, 4,4′-diformyl-1,1′-biphenyl, or 1,3,5-tris(4-formylphenyl)benzene) monomers. Such sp 2 carbon-jointed-pyridinyl frameworks, featuring crystalline honeycomb-like structures with high surface areas, enable driving two half-reactions of water splitting separately under visible light irradiation, comparable to graphitic carbon nitride (g-C 3 N 4 ) derivatives. Semiconducting covalent organic frameworks (COF) with conjugated structures are desired for optoelectric conversion but poor reversibility of bond forming reactions hampers the formation of crystalline structures. Here, the authors synthesise COFs with disubstituted C = C linkages which enable water splitting under visible light irradiation.

The generation of sustainable and stable semiconductors for solar energy conversion by photoredox catalysis, for example, light-induced water splitting and carbon dioxide reduction, is a key challenge of modern materials chemistry. Here we present a simple synthesis of a ternary semiconductor, boron carbon nitride, and show that it can catalyse hydrogen or oxygen evolution from water as well as carbon dioxide reduction under visible light illumination. The ternary B–C–N alloy features a delocalized two-dimensional electron system with sp 2 carbon incorporated in the h -BN lattice where the bandgap can be adjusted by the amount of incorporated carbon to produce unique functions. Such sustainable photocatalysts made of lightweight elements facilitate the innovative construction of photoredox cascades to utilize solar energy for chemical conversion. Metal-free semiconductors with appropriate bandgaps create photocatalytic routes to water splitting and CO 2 reduction. Here the authors dope hexagonal boron nitride nanosheets with carbon via a simple method to synthesize a ternary B–C–N alloy capable of performing just this function.

Large-scale photochemical synthesis of high value chemicals under mild conditions is an ideal method of green chemical production. However, a scalable photocatalytic process has been barely reported due to the costly preparation, low stability of photosensitizers and critical reaction conditions required for classical photocatalysts. Here, we report the merging of flow chemistry with heterogeneous photoredox catalysis for the facile production of high value compounds in a continuous flow reactor with visible light at room temperature in air. In the flow reactor system, polymeric carbon nitrides, which are cheap, sustainable and stable heterogeneous photocatalysts, are immobilized onto glass beads and fibers, demonstrating a highly flexible construction possibility for devices of the photocatalytic materials. As an example of the production of high value chemicals, important chemical structures such as cyclobutanes, which are basic building blocks for many pharmaceutical compounds, like magnosalin, are synthesized in flow with high catalytic efficiency and stability. Large-scale photochemical synthesis of high value chemicals is an ideal method of green chemical production. Here, the authors show the merging of heterogeneous carbon nitride photocatalysis with flow chemistry for the scalable organosynthesis of fine chemicals in a continuous flow reactor.

The visible-light-driven photocatalytic CO 2 reduction with high efficiency is highly desirable but challenging. Herein, we present porphyrin-tetraphenylethene-based covalent organic frameworks (MP-TPE-COF, where M=H 2 , Co and Ni; TPE=4,4′,4″,4‴-(ethane-1,1,2,2-tetrayl) tetrabenzaldehyde; COF=covalent organic framework) as ideal platforms for understanding photocatalytic CO 2 reduction at molecular level. Experimental and theoretical investigations have demonstrated crucial roles of metalloporphyrin units in selective adsorption, activation and conversion of CO 2 as well as in the separation of charge carriers and electron transfer, thus allowing for flexible modulation of photocatalytic activity and selectivity. CoP-TPE-COF exhibits high CO evolution rate of 2,414 µmol g −1 h −1 with the selectivity of 61% over H 2 generation under visible-light irradiation, while NiP-TPE-COF provides CO evolution rate of 525 µmol g −1 h −1 and 93% selectivity with superior durability. Moreover, the photocatalytic system is feasible for the simulated flue gas, which provides CO evolution rate of 386 µmol g −1 h −1 and selectivity of 77%. This work provides in-depth insight into the structure-activity relationships toward the activation and photoreduction of CO 2 .

To enhance the power supply reliability of the microgrid cluster consisting of AC/DC hybrid microgrids, this paper proposes an innovative structure that enables backup power to be accessed quickly in the event of power source failure. The structure leverages the quick response characteristics of thyristor switches, effectively reducing the power outage time. The corresponding control strategy is introduced in detail in this paper. Furthermore, taking practical considerations into account, two types of AC/DC hybrid microgrid structures are designed for grid-connected and islanded states. These microgrids exhibit strong distributed energy consumption capabilities, simple control strategies, and high power quality. Additionally, the aforementioned structures are constructed within the MATLAB/Simulink R2023a simulation software. Their feasibility is verified, and comparisons with the existing studies are conducted using specific examples. Finally, the cost and efficiency of the application of this study are discussed. Both the above results and analysis indicate that the structures proposed in this paper can reduce costs, improve efficiency, and enhance power supply stability.

In the past decade, research in the field of artificial photosynthesis has shifted from simple, inorganic semiconductors to more abundant, polymeric materials. For example, polymeric carbon nitrides have emerged as promising materials for metal-free semiconductors and metal-free photocatalysts. Polymeric carbon nitride (melon) and related carbon nitride materials are desirable alternatives to industrially used catalysts because they are easily synthesized from abundant and inexpensive starting materials. Furthermore, these materials are chemically benign because they do not contain heavy metal ions, thereby facilitating handling and disposal. In this Review, we discuss the building blocks of carbon nitride materials and examine how strategies in synthesis, templating and post-processing translate from the molecular level to macroscopic properties, such as optical and electronic bandgap. Applications of carbon nitride materials in bulk heterojunctions, laser-patterned memory devices and energy storage devices indicate that photocatalytic overall water splitting on an industrial scale may be realized in the near future and reveal a new avenue of ‘post-silicon electronics’. Carbon nitrides are potentially cheap and metal-free alternatives for catalysts, semiconductors, battery materials and memory devices. In this Review, we discuss the synthesis, design and morphology of these materials, and reflect on the ability of methods such as templating, etching, dye sensitization, heteroatom doping and co-polymerization, as well as the assembly of various heterojunctions, to improve device performance.