Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination.

Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocally demonstrated. Herein, we evidence the bifunctionality of carbons and metal sites in the acetylene hydrochlorination catalytic cycle.

Economic and Environmental Competitiveness of Ethane-Based Technologies for Vinyl Chloride Synthesis.

The synthesis of the vinyl chloride monomer (VCM), employed to manufacture poly(vinyl chloride) (PVC) plastic, primarily relies on oil-derived ethylene, resulting in high costs and carbon footprint. Natural gas-derived ethane in VCM synthesis has long been considered a transformative feedstock to lower emissions and expenses. In this work, we evaluate the environmental potential and economics of recently developed catalytic ethane chlorination technologies for VCM synthesis.

Challenges and Opportunities in Engineering the Electronic Structure of Single-Atom Catalysts.

Controlling the electronic structure of transition-metal single-atom heterogeneous catalysts (SACs) is crucial to unlocking their full potential. The ability to do this with increasing precision offers a rational strategy to optimize processes associated with the adsorption and activation of reactive intermediates, charge transfer dynamics, and light absorption. While several methods have been proposed to alter the electronic characteristics of SACs, such as the oxidation state, band structure, orbital occupancy, and associated spin, the lack of a systematic approach to their application makes it difficult to control their effects.

Controlled Formation of Dimers and Spatially Isolated Atoms in Bimetallic Au-Ru Catalysts via Carbon-Host Functionalization.

The introduction of a foreign metal atom in the coordination environment of single-atom catalysts constitutes an exciting frontier of active-site engineering, generating bimetallic low-nuclearity catalysts often exhibiting unique catalytic synergies. To date, the exploration of their full scope is thwarted by (i) the lack of synthetic techniques with control over intermetallic coordination, and (ii) the challenging characterization of these materials. Herein, carbon-host functionalization is presented as a strategy to selectively generate Au-Ru dimers and isolated sites by simple incipient wetness impregnation, as corroborated by careful X-ray absorption spectroscopy analysis.