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Single-atom catalysts anchoring offers a desirable pathway for efficiency maximization and cost-saving for photocatalytic hydrogen evolution. However, the single-atoms loading amount is always within 0.5% in most of the reported due to the agglomeration at higher loading concentrations. In this work, the highly dispersed and large loading amount (>1 wt%) of copper single-atoms were achieved on TiO 2 , exhibiting the H 2 evolution rate of 101.7 mmol g −1  h −1 under simulated solar light irradiation, which is higher than other photocatalysts reported, in addition to the excellent stability as proved after storing 380 days. More importantly, it exhibits an apparent quantum efficiency of 56% at 365 nm, a significant breakthrough in this field. The highly dispersed and large amount of Cu single-atoms incorporation on TiO 2 enables the efficient electron transfer via Cu 2+ -Cu + process. The present approach paves the way to design advanced materials for remarkable photocatalytic activity and durability. In this work, the highly dispersed and large loading amount (>1 wt%) of copper single-atoms were achieved on TiO 2 , resulting into an apparent quantum efficiency of 56% at 365 nm, in addition to an excellent thermal stability as proved after storing 380 days.

Methane (CH 4 ) oxidation to high value chemicals under mild conditions through photocatalysis is a sustainable and appealing pathway, nevertheless confronting the critical issues regarding both conversion and selectivity. Herein, under visible irradiation (420 nm), the synergy of palladium (Pd) atom cocatalyst and oxygen vacancies (OVs) on In 2 O 3 nanorods enables superior photocatalytic CH 4 activation by O 2 . The optimized catalyst reaches ca. 100 μmol h −1 of C1 oxygenates, with a selectivity of primary products (CH 3 OH and CH 3 OOH) up to 82.5%. Mechanism investigation elucidates that such superior photocatalysis is induced by the dedicated function of Pd single atoms and oxygen vacancies on boosting hole and electron transfer, respectively. O 2 is proven to be the only oxygen source for CH 3 OH production, while H 2 O acts as the promoter for efficient CH 4 activation through ·OH production and facilitates product desorption as indicated by DFT modeling. This work thus provides new understandings on simultaneous regulation of both activity and selectivity by the synergy of single atom cocatalysts and oxygen vacancies. CH4 oxidation to high value chemicals under mild conditions through photocatalysis confronts critical issues regarding both conversion and selectivity. Here, atomic Pd and oxygen vacancies were integrated on In2O3 nanorods, leading to visible-driven CH4 conversion with a remarkable yield of oxygenates and high selectivity of primary products.

Solar-driven CO 2 reduction by abundant water to alcohols can supply sustainable liquid fuels and alleviate global warming. However, the sluggish water oxidation reaction has been hardly reported to be efficient and selective in CO 2 conversion due to fast charge recombination. Here, using transient absorption spectroscopy, we demonstrate that microwave-synthesised carbon-dots ( m CD) possess unique hole-accepting nature, prolonging the electron lifetime ( t 50% ) of carbon nitride (CN) by six folds, favouring a six-electron product. m CD-decorated CN stably produces stoichiometric oxygen and methanol from water and CO 2 with nearly 100% selectivity to methanol and internal quantum efficiency of 2.1% in the visible region, further confirmed by isotopic labelling. Such m CD rapidly extracts holes from CN and prevents the surface adsorption of methanol, favourably oxidising water over methanol and enhancing the selective CO 2 reduction to alcohols. This work provides a unique strategy for efficient and highly selective CO 2 reduction by water to high-value chemicals. Solar-driven CO2 reduction by abundant water to alcohols is hindered by the sluggish water oxidation reaction. Here, the authors demonstrate that the microwave-synthesized carbon-dots possess unique hole-accepting nature, allowing stoichiometric oxygen and methanol production from water and CO2 with nearly 100% selectivity to methanol.

Photocatalytic CO 2 conversion promises an ideal route to store solar energy into chemical bonds. However, sluggish electron kinetics and unfavorable product selectivity remain unresolved challenges. Here, an ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate, and borate-anchored Co single atoms were separately loaded on ultrathin g-C 3 N 4 nanosheets. The optimized nanocomposite photocatalyst produces CO and CH 4 from CO 2 and water under UV–vis light irradiation, exhibiting a 42-fold photoactivity enhancement compared with g-C 3 N 4 and nearly 100% selectivity towards CO 2 reduction. Experimental and theoretical results reveal that the ionic liquid extracts electrons and facilitates CO 2 reduction, whereas Co single atoms trap holes and catalyze water oxidation. More importantly, the maximum electron transfer efficiency for CO 2 photoreduction, as measured with in-situ μs-transient absorption spectroscopy, is found to be 35.3%, owing to the combined effect of the ionic liquid and Co single atoms. This work offers a feasible strategy for efficiently converting CO 2 to valuable chemicals. There is growing interest in designing photocatalysts for CO 2 conversion. Here, the authors combine an ionic liquid with Co single atoms as dual-cocatalysts for g-C 3 N 4 , accelerating electron kinetics and improving CO 2 reduction selectivity.

Direct solar-driven methane (CH 4 ) reforming is highly desirable but challenging, particularly to achieve a value-added product with high selectivity. Here, we identify a synergistic ensemble effect of atomically dispersed copper (Cu) species and partially reduced tungsten (W δ+ ), stabilised over an oxygen-vacancy-rich WO 3 , which enables exceptional photocatalytic CH 4 conversion to formaldehyde (HCHO) under visible light, leading to nearly 100% selectivity, a very high yield of 4979.0 μmol·g −1 within 2 h, and the normalised mass activity of 8.5 × 10 6  μmol·g -1 Cu ·h −1 of HCHO at ambient temperature. In-situ EPR and XPS analyses indicate that the Cu species serve as the electron acceptor, promoting the photo-induced electron transfer from the conduction band to O 2 , generating reactive •OOH radicals. In parallel, the adjacent W δ+ species act as the hole acceptor and the preferred adsorption and activation site of H 2 O to produce hydroxyl radicals (•OH), and thus activate CH 4 to methyl radicals (•CH 3 ). The synergy of the adjacent dual active sites boosts the overall efficiency and selectivity of the conversion process. Direct solar-driven methane (CH 4 ) reforming is highly desirable but challenging. Here, the synergy of atomic Cu species and partially reduced tungsten (W δ+ ), stabilized over an oxygen-vacancy-rich WO 3 , enables exceptional CH 4 conversion to formaldehyde (HCHO) under visible light.

Direct methane conversion to high-value chemicals under mild conditions is attractive yet challenging due to the inertness of methane and the high reactivity of valuable products. This work presents an efficient and selective strategy to achieve direct methane conversion through the oxidative coupling of methane over a visible-responsive Au-loaded CeO 2 by photon-phonon co-driven catalysis. A record-high ethane yield of 755 μmol h −1 (15,100 μmol g −1 h −1 ) and selectivity of 93% are achieved under optimised reaction conditions, corresponding to an apparent quantum efficiency of 12% at 365 nm. Moreover, the high activity of the photocatalyst can be maintained for at least 120 h without noticeable decay. The pre-treatment of the catalyst at relatively high temperatures introduces oxygen vacancies, which improves oxygen adsorption and activation. Furthermore, Au, serving as a hole acceptor, facilitates charge separation, inhibits overoxidation and promotes the C-C coupling reaction. All these enhance photon efficiency and product yield. To achieve high yield and selectivity of C 2+ products from methane conversion, the authors report a photon-phonon co-driven catalytic process using CeO 2 catalysts. Gold, as a co-catalyst, promotes C-C coupling and suppresses overoxidation

Phenol is one of the most important fine chemical intermediates in the synthesis of plastics and drugs with a market size of ca . $30b 1 and the commercial production is via a two-step selective oxidation of benzene, requiring high energy input (high temperature and high pressure) in the presence of a corrosive acidic medium, and causing serious environmental issues 2 – 5 . Here we present a four-phase interface strategy with well-designed Pd@Cu nanoarchitecture decorated TiO 2 as a catalyst in a suspension system. The optimised catalyst leads to a turnover number of 16,000–100,000 for phenol generation with respect to the active sites and an excellent selectivity of ca . 93%. Such unprecedented results are attributed to the efficient activation of benzene by the atomically Cu coated Pd nanoarchitecture, enhanced charge separation, and an oxidant-lean environment. The rational design of catalyst and reaction system provides a green pathway for the selective conversion of symmetric organic molecules. Phenol is one of the most important fine chemicals, but its synthesis is highly energy intensive. Here, the authors report an economical pathway for the selective photocatalytic conversion of benzene to phenol in high yield and selectivity by Pd@Cu/TiO 2 catalyst using with air as oxidant.

The selective oxidative dehydrogenation of ethane (ODHE) is attracting increasing attention as a method for ethylene production. Typically, thermocatalysts operating at high temperatures are needed for C–H activation in ethane. In this study, we describe a low temperature ( < 140 °C) photocatalytic route for ODHE, using O 2 as the oxidant. A photocatalyst containing PdZn intermetallic nanoparticles supported on ZnO is prepared, affording an ethylene production rate of 46.4 mmol g –1  h –1 with 92.6% ethylene selectivity under 365 nm irradiation. When we employ a simulated shale gas feed, the photocatalytic ODHE system achieves nearly 20% ethane conversion while maintaining an ethylene selectivity of about 87%. The robust interface between the PdZn intermetallic nanoparticles and ZnO support plays a crucial role in ethane activation through a photo-assisted Mars-van Krevelen mechanism, followed by a rapid lattice oxygen replenishment to complete the reaction cycle. Our findings demonstrate that photocatalytic ODHE is a promising method for alkane-to-alkene conversions under mild conditions. The selective oxidative dehydrogenation of ethane is attracting increasing attention as a method for ethylene production. Here, PdZn supported on ZnO affords record-breaking photocatalytic ethane-to-ethylene conversion rate, emphasizing the pivotal role of the interface between PdZn and ZnO in the process.

Methane activation by photocatalysis is one of the promising sustainable technologies for chemical synthesis. However, the current efficiency and stability of the process are moderate. Herein, a PdCu nanoalloy (~2.3 nm) was decorated on TiO 2 , which works for the efficient, stable, and selective photocatalytic oxidative coupling of methane at room temperature. A high methane conversion rate of 2480 μmol g −1 h −1 to C 2 with an apparent quantum efficiency of ~8.4% has been achieved. More importantly, the photocatalyst exhibits the turnover frequency and turnover number of 116 h −1 and 12,642 with respect to PdCu, representing a record among all the photocatalytic processes (λ > 300 nm) operated at room temperature, together with a long stability of over 112 hours. The nanoalloy works as a hole acceptor, in which Pd softens and weakens C-H bond in methane and Cu decreases the adsorption energy of C 2 products, leading to the high efficiency and long-time stability. Efficient and stable photocatalytic oxidative coupling of methane to C2 products is revealed by Tang’s group via synergistic effects of a PdCu nanoalloy cocatalyst which achieves high TON PdCu of 12642 and TOF PdCu of 116 h −1 with >100 hour stability.

Precisely controlled deuterium labeling at specific sites of N -alkyl drugs is crucial in drug-development as over 50% of the top-selling drugs contain N -alkyl groups, in which it is very challenging to selectively replace protons with deuterium atoms. With the goal of achieving controllable isotope-labeling in N -alkylated amines, we herein rationally design photocatalytic water-splitting to furnish [H] or [D] and isotope alkanol-oxidation by photoexcited electron-hole pairs on a polymeric semiconductor. The controlled installation of N -CH 3, -CDH 2, -CD 2 H, -CD 3 , and - 13 CH 3 groups into pharmaceutical amines thus has been demonstrated by tuning isotopic water and methanol. More than 50 examples with a wide range of functionalities are presented, demonstrating the universal applicability and mildness of this strategy. Gram-scale production has been realized, paving the way for the practical photosynthesis of pharmaceuticals. Controllable deuteration of N-alkyl amines is crucial in drug-development as they constitute over 50% of the top-selling drugs. Here, the authors report a polymeric semiconductor acting as photocatalyst in water-splitting and in isotope alkanol-oxidation by photoexcited electron-hole pairs, and furnishing deuterated amines.