Catalyst systems populated by high-density single atoms are crucial for improving catalytic activity and selectivity, which can potentially maximize the industrial prospects of heterogeneous single-atom catalysts (SACs). However, achieving high-loading SACs with metal contents above 10 wt% remains challenging. Here we describe a general negative pressure annealing strategy to fabricate ultrahigh-loading SACs with metal contents up to 27.3–44.8 wt% for 13 different metals on a typical carbon nitride matrix. Furthermore, our approach enables the synthesis of high-entropy single-atom catalysts (HESACs) that exhibit the coexistence of multiple metal single atoms with high metal contents. In-situ aberration-corrected HAADF-STEM (AC-STEM) combined with ex-situ X-ray absorption fine structure (XAFS) demonstrate that the negative pressure annealing treatment accelerates the removal of anionic ligand in metal precursors and boosts the bonding of metal species with N defective sites, enabling the formation of dense N-coordinated metal sites. Increasing metal loading on a platinum (Pt) SAC to 41.8 wt% significantly enhances the activity of propane oxidation towards liquid products, including acetone, methanol, and acetic acid et al. This work presents a straightforward and universal approach for achieving many low-cost and high-density SACs for efficient catalytic transformations.

Electrocatalytic acetylene semi-hydrogenation to ethylene powered by renewable electricity represents a sustainable pathway, but the inadequate current density and single-pass yield greatly impedes the production efficiency and industrial application. Herein, we develop a F-modified Cu catalyst that shows an industrial partial current density up to 0.76 A cm⁻² with an ethylene Faradic efficiency surpass 90%, and the maximum single-pass yield reaches a notable 78.5%. Furthermore, the Cu-F showcase the capability to directly convert acetylene into polymer-grade ethylene in a tandem flow cell, almost no acetylene residual in the production. Combined characterizations and calculations reveal that the Cu^δ+ (near fluorine) enhances the water dissociation, and the generated active hydrogen are immediately transferred to Cu⁰ (away from fluorine) and react with the locally adsorbed acetylene. Therefore, the hydrogen evolution reaction is surpassed and the overall acetylene semi-hydrogenation performance is boosted. Our findings provide new opportunity towards rational design of catalysts for large-scale electrosynthesis of ethylene and other important industrial raw.