Single-Atom and Dual-Atom Electrocatalysts: Synthesis and Applications.

Distinguishing themselves from nanostructured catalysts, single-atom catalysts (SACs) typically consist of positively charged single metal and coordination atoms without any metal-metal bonds. Dual-atom catalysts (DACs) have emerged as extended family members of SACs in recent years. Both SACs and DACs possess characteristics that combine both homogeneous and heterogeneous catalysis, offering advantages such as uniform active sites and adjustable interactions with ligands, while also inheriting the high stability and recyclability associated with heterogeneous catalyst systems. They offer numerous advantages and are extensively utilized in the field of electrocatalysis, so they have emerged as one of the most prominent material research platforms in the direction of electrocatalysis. This review provides a comprehensive review of SACs and DACs in the field of electrocatalysis: encompassing economic production, elucidating electrocatalytic reaction pathways and associated mechanisms, uncovering structure-performance relationships, and addressing major challenges and opportunities within this domain. Our objective is to present novel ideas for developing advanced synthesis strategies, precisely controlling the microstructure of catalytic active sites, establishing accurate structure-activity relationships, unraveling potential mechanisms underlying electrocatalytic reactions, identifying more efficient reaction paths, and enhancing overall performance in electrocatalytic reactions.

Highly Selective Carbonylation of CH3 Cl to Acetic Acid Catalyzed by Pyridine-Treated MOR Zeolite.

The selective conversion of methane to high value-added chemicals under mild conditions is of great significance for the commercially viable and sustainable utilization of methane but remains a formidable challenge. Herein, we report a strategy for efficiently converting methane to acetic acid via CH3 Cl as an intermediate. Up to 99.3 % acetic acid and methyl acetate (AA+MA) selectivity was achieved over pyridine-pretreated MOR (MOR-8) under moderate conditions of 523 K and 2.0 MPa. Water, conventionally detrimental to carbonylation reaction over zeolite catalysts, was conducive to the production of AA in the current reaction system. In the 100 h continuous test with the MOR-8 catalyst, the average AA+MA selectivity remained over 98 %. AA was formed by carbonylation of methoxy groups within 8-membered rings of MOR followed by hydrolysis. This strategy provided an approach for highly efficient utilization of methane to oxygenates under mild reaction conditions.

Highly Enhanced Aromatics Selectivity by Coupling of Chloromethane and Carbon Monoxide over H-ZSM-5.

The transformation of methane into high value-added chemicals such as aromatics provides a more desired approach towards sustainable chemistry but remains a critical challenge due to the low selectivity of aromatics and poor stability. Herein, we first report a coupling reaction of CH3 Cl and CO (CCTA) based on methane conversion, which achieves extremely high aromatics selectivity (82.2 %) with the selectivity of BTX up to ca. 60 % over HZSM-5. The promoting effects have been demonstrated on other zeolites especially 10-membered rings (10 MR) zeolites. Multiple characterizations show that 2,3-dimethyl-2-cyclopentene-1-one (DMCPO) is generated from acetyl groups and olefins. Furthermore, isotopic labeling analysis confirms that CO is inserted into the DMCPO and aromatics rings. A new aromatization mechanism is proposed, including the formation of the above intermediates, which conspicuously weakens the hydrogen transfer reaction, leading to a considerable increase of aromatics selectivity and a dramatic drop in alkanes.