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Single-atom catalysts (SACs) have become a prominent theme in heterogeneous catalysis, not least because of the potential fundamental insight into active sites. The desired level of understanding, however, is prohibited due to the inhomogeneity of most supported SACs and the lack of suitable tools for structure-activity correlation studies with atomic resolution. Herein, we describe the potency of electrospray ionization mass spectrometry (ESI-MS) to study molecularly defined SACs supported on polyoxometalates in catalytic reactions. We identified the exact composition of active sites and their evolution in the catalytic cycle during CO and alcohol oxidation reactions performed in the liquid phase. Critical information on metal-dependent reaction mechanisms, the key intermediates, the dynamics of active sites and even the stepwise activation barriers were obtained, which would be challenging to gather via prevailingly adopted techniques in SAC research. DFT calculations revealed intricate details of the reaction mechanisms, and strong synergies between ESI-MS defined SAC sites and electronic structure theory calculations become apparent.

The photocatalytic conversion of biomass and plastic waste provides opportunities for sustainable fuel and chemical production. Heterogeneous photocatalysts, typically composed of semiconductors with distinctive redox properties in their conduction band (CB) and valence band (VB), facilitate both the oxidative and reductive valorization of organic feedstocks. This article provides a comprehensive overview of recent advancements in the photorefinery of biomass and plastics from the perspective of the redox properties of photocatalysts. We explore the roles of the VB and CB in enhancing the value‐added conversion of biomass and plastics via various pathways. Our aim is to bridge the gap between photocatalytic mechanisms and renewable carbon feedstock valorization, inspiring further development in photocatalytic refinery of biomass and plastics. [ABSTRACT FROM AUTHOR]

Achieving efficient catalytic conversion over a heterogeneous catalyst with excellent resistance against leaching is still a grand challenge for sustainable chemical synthesis in aqueous solution. Herein, we devised a single‐atom Pt1/hydroxyapatite (HAP) catalyst via a simple hydrothermal strategy. Gratifyingly, this robust Pt1/HAP catalyst exhibits remarkable catalytic selectivity and catalyst stability for the selective oxidation of C2–C4 polyols to corresponding primary hydroxy acids. It is found that the Pt−(O−P) linkages with strong electron‐withdrawing function of PO43− (Pt1−OPO43− pair active site) not only realize the activation of the C−H bond, but also destabilize the transition state from adsorbed hydroxy acids toward the C−C cleavage, resulting in the sharply increased selectivity of hydroxy acids. Moreover, the strong PO43−‐coordination effect provides electrostatic stabilization for single‐atom Pt, ensuring the highly efficient catalysis of Pt1/HAP for over 160 hours with superior leaching resistance. [ABSTRACT FROM AUTHOR]

The upgrading of plastic waste is one of the grand challenges for the 21st century owing to its disruptive impact on the environment. Here, we show the first example of the upgrading of various aromatic plastic wastes with C−O and/or C−C linkages to arenes (75–85 % yield) via catalytic hydrogenolysis over a Ru/Nb2O5 catalyst. This catalyst not only allows the selective conversion of single‐component aromatic plastic, and more importantly, enables the simultaneous conversion of a mixture of aromatic plastic to arenes. The excellent performance is attributed to unique features including: (1) the small sized Ru clusters on Nb2O5, which prevent the adsorption of aromatic ring and its hydrogenation; (2) the strong oxygen affinity of NbOx species for C−O bond activation and Brønsted acid sites for C−C bond activation. This study offers a catalytic path to integrate aromatic plastic waste back into the supply chain of plastic production under the context of circular economy. [ABSTRACT FROM AUTHOR]

A CO2‐mediated hydrogen storage energy cycle is a promising way to implement a hydrogen economy, but the exploration of efficient catalysts to achieve this process remains challenging. Herein, sub‐nanometer Pd–Mn clusters were encaged within silicalite‐1 (S‐1) zeolites by a ligand‐protected method under direct hydrothermal conditions. The obtained zeolite‐encaged metallic nanocatalysts exhibited extraordinary catalytic activity and durability in both CO2 hydrogenation into formate and formic acid (FA) dehydrogenation back to CO2 and hydrogen. Thanks to the formation of ultrasmall metal clusters and the synergic effect of bimetallic components, the PdMn0.6@S‐1 catalyst afforded a formate generation rate of 2151 molformate molPd−1 h−1 at 353 K, and an initial turnover frequency of 6860 molH2 molPd−1 h−1 for CO‐free FA decomposition at 333 K without any additive. Both values represent the top levels among state‐of‐the‐art heterogeneous catalysts under similar conditions. This work demonstrates that zeolite‐encaged metallic catalysts hold great promise to realize CO2‐mediated hydrogen energy cycles in the future that feature fast charge and release kinetics. [ABSTRACT FROM AUTHOR]

We report a NaOH-mediated NaBH4 reduction method for the synthesis of mono-, bi-, and tri-thiolate-protected Au25 nanoclusters (NCs) with precise control of both the Au core and thiolate ligand surface. The key strategy is to use NaOH to tune the formation kinetics of Au NCs, i.e., reduce the reduction ability of NaBH4 and accelerate the etching ability of free thiolate ligands, leading to a well-balanced reversible reaction for rapid formation of thermodynamically favorable Au25 NCs. This protocol is facile, rapid (≤3 h), versatile (applicable for various thiolate ligands), and highly scalable (>1 g Au NCs). In addition, bi- and tri-thiolate-protected Au25 NCs with adjustable ratios of hetero-thiolate ligands were easily obtained. Such ligand precision in molecular ratios, spatial distribution and uniformity resulted in richly diverse surface landscapes on the Au NCs consisting of multiple functional groups such as carboxyl, amine, and hydroxy. Analysis based on NMR spectroscopy revealed that the hetero-ligands on the NCs are well distributed with no ligand segregation. The unprecedented synthesis of multi-thiolate-protected Au25 NCs may further promote the practical applications of functional metal NCs. [ABSTRACT FROM AUTHOR]

Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2‐O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 μmolgPTA-1h-1 ${\mu mol\ {g}_{PTA}^{-1}{h}^{-1}}$ with approximately 20.3 % overall electron yield. Under continuous operation, we achieved 19.90 μmolgPTA-1h-1 ${\mu mol\ {g}_{PTA}^{-1}{h}^{-1}}$ catalytic activity, over 74.3 % methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo‐ and electrochemical methane oxidation at ambient conditions. [ABSTRACT FROM AUTHOR]