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Solar-driven transfer hydrogenation of unsaturated bonds has received considerable attention in the research area of sustainable organic synthesis; however, water, the ultimate green source of hydrogen, has rarely been investigated due to the high barrier associated with splitting of water molecules. We report a carbon-nitride-supported palladium single-atom heterogeneous catalyst with unparalleled performance in photocatalytic water-donating transfer hydrogenation compared to its nanoparticle counterparts. Isotopic-labeling experiments and operando nuclear magnetic resonance measurements confirm the direct hydrogenation mechanism using in situ-generated protons from water splitting under visible-light irradiation. Density functional theory calculations attribute the high activity to lower barriers for hydrogenation, facilitated desorption of ethylbenzene, and facile hydrogen replenishment from water on the atomic palladium sites.

As a state-of-the-art conjugated polymer photocatalyst, graphitic carbon nitride(abbreviated as g-C3N4) has shown great potential in photocatalytic cofactor(reduced form of nicotinamide adenine dinucleotide, NADH) regeneration. Herein, Fe-doped g-C3N4 was engineered for photocatalytic NADH oxidation. The π-π interaction between the NADH molecule and the conjugated heptazine building block facilitates the adsorption of NADH onto the framework, as revealed by density functional theory(DFT) calculations. Furthermore, iron doping promoted the oxidation kinetics of NADH under blue LED illumination. The conversion ratio of NADH to its oxidized form could be up to 85.7% in 20 min, comparing with 59.4% for metal-free counterpart. Enzyme assay employing formate dehydrogenase(FDH) further verified the selectivity of the products, with 67.5%±2.6% of enzymatically active 1,4-NADH being regenerated following the oxidation process. Scavenger experiments suggest the dominant role of photo-induced electrons in the oxidation of NADH. This work could shed light on developing a novel cofactor regeneration route through the synergistic effect between the metal doping and noncovalent interaction based on the conjugated polymer.

Pristine graphitic carbon nitride (g-C3N4) suffers from poor photocatalytic activity due to its limited light adsorption, small specific surface area and feasible recombination of photogenerated charge carriers. One practical approach to solve the problem of low solar-to-hydrogen efficiency is nanostructuring the morphology of g-C3N4 to enhance its light-harvesting property and boost the rate of charge-carrier transportation. Here, we present a strategy to optimize the textural properties and catalytic performance of g-C3N4 via using oxamide (OA) as a chemical modifier in the precursor solution, which significantly make the light absorption edge shift from 440 to 650 nm. Moreover, the nanostructure of the resultant g-C3N4 can be easily tuned with increasing the amount of oxamide. The morphological features of g-C3N4 materials change from sheet-like structure to tubular structure, porous nanotube and eventually interconnected porous sheet. More interestingly, the unique g-C3N4 nanostructure offers advantages of a broader solar absorption spectrum and accelerates charge carrier dynamics that are favorable for advancing photocatalytic performance. The findings provide insightful information that can be used to understand the structure-property relationship in g-C3N4 nanostructures for improved solar-to-fuel conversion.

Ultrasmall and homogeneous bimetallic PdxBi nanoalloys are well distributed on a Vulcan carbon support by a facile, low-cost synthetic strategy. The electrochemical activity of the as-prepared homogeneous PdxBi nanoalloy/carbon black nanocomposites is closely related to the content of Bi, revealing their excellent electrocatalytic performance for selective oxidation of monohydric alcohols and vicinal diols in alkali medium.

The ability to tailor the properties of metal centers in single-atom heterogeneous catalysts depends on the availability of advanced approaches for characterization of their structure. Except for specific host materials with well-defined metal adsorption sites, determining the local atomic environment remains a crucial challenge, often relying heavily on simulations. This article reports an advanced analysis of platinum atoms stabilized on poly(triazine imide), a nanocrystalline form of carbon nitride. The approach discriminates the distribution of surface coordination sites in the host, the evolution of metal coordination at different stages during the synthesis of the material, and the potential locations of metal atoms within the lattice. Consistent with density functional theory predictions, simultaneous high-resolution imaging in high-angle annular dark field and bright field modes experimentally confirms the preferred localization of platinum in-plane in the corners of the triangular cavities. X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and dynamic nuclear polarization enhanced 15N nuclear magnetic resonance (DNP-NMR) spectroscopies coupled with density functional theory (DFT) simulations reveal that the predominant metal species comprise Pt(II) bound to three nitrogen atoms and one chlorine atom inside the coordination sites. The findings, which narrow the gap between experimental and theoretical elucidation, contribute to the improved structural understanding and provide a benchmark for exploring the speciation of single-atom catalysts based on carbon nitrides.

Isolated atoms featuring unique reactivity are at the heart of enzymatic and homogeneous catalysts. In contrast, although the concept has long existed, single-atom heterogeneous catalysts (SACs) have only recently gained prominence. Host materials have similar functions to ligands in homogeneous catalysts, determining the stability, local environment, and electronic properties of isolated atoms and thus providing a platform for tailoring heterogeneous catalysts for targeted applications. Within just a decade, we have witnessed many examples of SACs both disrupting diverse fields of heterogeneous catalysis with their distinctive reactivity and substantially enriching our understanding of molecular processes on surfaces. To date, the term SAC mostly refers to late transition metal-based systems, but numerous examples exist in which isolated atoms of other elements play key catalytic roles. This review provides a compositional encyclopedia of SACs, celebrating the 10th anniversary of the introduction of this term. By defining single-atom catalysis in the broadest sense, we explore the full elemental diversity, joining different areas across the whole periodic table, and discussing historical milestones and recent developments. In particular, we examine the coordination structures and associated properties accessed through distinct single-atom-host combinations and relate them to their main applications in thermo-, electro-, and photocatalysis, revealing trends in element-specific evolution, host design, and uses. Finally, we highlight frontiers in the field, including multimetallic SACs, atom proximity control, and possible applications for multistep and cascade reactions, identifying challenges, and propose directions for future development in this flourishing field.

Journal of Materials Chemistry A, 5 (31), ISSN:2050-7488, ISSN:2050-7496

Carbon nitrides are promising hosts for single-atom catalysts (SACs) based on small amounts of precious metals dispersed as isolated atoms, presenting tantalizing opportunities to reduce the cost a...

Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom-efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non-scalable regime in which each atom counts. Almost all trends in this ultra-small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence applicationdependent requirements of the active ensemble. In the semihydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well-defined numbers of atoms.

Ammonium chloride can serve as a green, unreactive and reusable template to prepare heptazine-based graphitic carbon nitrides with surface areas up to 30 m2 g−1 and up to 6 times higher photocatalytic activity, by a simplified procedure that comprises only pyrolysis of the reaction mixture containing precursor and salt.

Graphitic carbon nitride (CN) has been widely regarded as a promising photocatalyst since the discovery of its capability for photocatalytic hydrogen evolution. Herein, we developed a functional CN film on a conductive fluorine‐doped tin oxide (FTO) electrode by using a microprinting‐based direct growth method. Furthermore, the photoelectrochemical performance of the derived CN@FTO film was demonstrated to be enhanced by incorporating molecular cobalt species. The reduced charge transport resistance in the cobalt‐modified CN@FTO films is suggested to accelerate the charge‐carrier transfer rate and thus to improve the performance in photoelectrochemical application. The approach is versatile and can be further optimized by selecting a proper “ink” solution and modifier on various conductive substrates.

Carbon nitride polymers were prepared for the first time by the pyrolysis of 3,5-disubstituted-1,2,4-triazole derivatives, namely 3,5-diamino-1,2,4-triazole [1] and 3-amino-1,2,4-triazole-5-thiol [2], in bulk as well as in LiCl/KCl salt melts. The reaction of [1] and [2] in bulk yields condensed heptazine-based polymers, while in LiCl/KCl eutectics it leads to the formation of well-defined potassium poly(heptazine imides), according to the results of 13C NMR and XPS investi-gations, whose formation resembles that of emeraldine salts of polyaniline. The density functional calculations supported the structural model suggested for potassium poly(heptazine imide) polymer. Owing to the specific reaction path, the products obtained from triazoles therefore show electronic properties rather different to known carbon nitrides, such as band gap and conduction and valence bands positions. With the degree of crystallinity of the reference materials, triazole-derived carbon nitrides are characterized by almost complete absence of steady photoluminescence, charge separation and localization upon excitation seems to be improved. As a consequence, photocatalysts prepared from [2] outperform classical carbon nitrides in a model dye degradation reaction and mesoporous graphitic carbon nitride in hydrogen evolution reaction under visible light irradiation. On its turn, [1] can be conveniently used as a co-monomer in order to prepare carbon nitrides with improved visible light absorption.

Electronic structures of semiconductor photocatalysts control the light absorbance, charge-carrier separation and mobility, activation energy and consequently, photocatalytic activity. Ion doping has been widely used to modify the electronic structure of a semiconductor photocatalyst. Here, we successfully synthesized Sn doped single crystalline anatase TiO2 particles dominated with {1 0 5} facets by a gas phase oxidation process, and their structure and composition were thoroughly analyzed by XRD/TEM/FESEM/XPS. The photoluminescence emission spectra measurements reveal that the small amount of doped Sn in TiO2 could suppress the recombination of photogenerated electron–hole pairs. Thus, the Sn doped TiO2 shows a significantly enhanced photocatalytic hydrogen evolution performance, with its hydrogen generation rate being 4.5 times higher than that of pure TiO2. First-principle simulation results suggest the doped Sn at the edge exhibit higher adsorption energy toward H, which could promote the H2 generation from the splitting of water.

Dye-sensitized solar cells (DSCs) are promising alternatives to conventional silicon devices because of their simple fabrication procedure, low cost, and high efficiency. Platinum is generally used as a superior counter electrode (CE) material, but the disadvantages such as high cost and low abundance greatly restrict the large-scale application of DSCs. An efficient and sustainable way to overcome the limited supply of Pt is the development of high-efficiency Pt-free CE materials, which should possess both high electrical conductivity and superior electrocatalytic activity simultaneously. Herein, for the first time, a two-step strategy to synthesize ruthenium dioxide (RuO2) nanocrystals is reported, and it is shown that RuO2 catalysts exhibit promising electrocatalytic activity towards triiodide reduction, which results in comparable energy conversion efficiency to that of conventional Pt CEs. More importantly, by virtue of first-principles calculations, the catalytic mechanism of electrocatalysis for triiodide reduction on various CEs is investigated systematically and it is found that the electrochemical triiodide reduction reaction on RuO2 catalyst surfaces can be enhanced significantly, owing to the ideal combination of good electrocatalytic activity and high electrical conductivity.

Carbon nitrides with the increased surface areas (≈90 m(2) g(-1)) were prepared by the heat-treatment of melamine-[Al(NO3)3]⋅9 H2O complexes. Here, [Al(NO3)3]⋅9 H2O was successfully used as a "green template" and a hydrogen-bonding partner of melamine, simultaneously providing a distinct porosity and defined particle morphology for the resulting carbon nitrides. The influence of the solvent and precursors ratio on the stoichiometry of the complexes, as well as the morphology, optical properties, and photocatalytic activity of resulting products for Rhodamine B degradation and sacrificial hydrogen evolution were investigated. We also studied the temperature-induced transformations of the starting complex to access the reaction mechanism. The developed synthesis procedure results in a significantly increased photocatalytic activity (up to 20-fold) compared with that of the ground reference material.

We report the preparation and hydrogenation performance of a single-site palladium catalyst that was obtained by the anchoring of Pd atoms into the cavities of mesoporous polymeric graphitic carbon nitride. The character- ization of the material confirmed the atomic dispersion of the palladium phase throughout the sample. The catalyst was applied for three-phase hydrogenations of alkynes and nitro- arenes in a continuous-flow reactor, showing its high activity and product selectivity in comparison with benchmark cata- lysts based on nanoparticles. Density functional theory calcu- lations provided fundamental insights into the material struc- ture and attributed the high catalyst activity and selectivity to the facile hydrogen activation and hydrocarbon adsorption on atomically dispersed Pd sites.

Multicomponent Cu-Cu2O-TiO2 nanojunction systems were successfully synthesized by a mild chemical process, and their structure and composition were thoroughly analyzed by X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The as-prepared Cu-Cu2O-TiO2 (3 and 9 h) nanojunctions demonstrated higher photocatalytic activities under UV/Vis light irradiation in the process of the degradation of organic compounds than those of the Cu-Cu2O, Cu-TiO2, and Cu2O-TiO2 starting materials. Moreover, time-resolved photoluminescence spectra demonstrated that the quenching times of electrons and holes in Cu-Cu2O-TiO2 (3 h) is higher than that of Cu-Cu2O-TiO2 (9 h); this leads to a better photocatalytic performance of Cu-Cu2O-TiO2 (3 h). The improvement in photodegradation activity and electron-hole separation of Cu-Cu2O-TiO2 (3 h) can be ascribed to the rational coupling of components and dimensional control. Meanwhile, an unusual electron-hole transmission pathway for photocatalytic reactions over Cu-Cu2O-TiO2 nanojunctions was also identified.

Novel assembly ultrathin PbBiO2Br nanosheets were synthesized by a facile solvothermal method. Structural characterizations indicate that the quaternary oxyhalide compound with a thickness of 8–9 nm can assemble into a hierarchical architecture. The e−–h+ pairs can separate efficiently in such a 2D structure, so that ultrathin PbBiO2Br nanosheets exhibit superior photocatalytic activity towards the degradation of organic contaminants under visible light.