Atomic Cobalt–Silver Dual-Metal Sites Confined on Carbon Nitride with Synergistic Ag Nanoparticles for Enhanced CO₂ Photoreduction

Abstract

Photocatalytic reduction of CO 2 to value-added solar fuels is of great significance to alleviate the severe environmental and energy crisis. Herein, we report the construction of a synergistic silver nanoparticle catalyst with adjacent atomic cobalt−silver dual-metal sites on P-doped carbon nitride (Co 1 Ag (1+n) −PCN) for photocatalytic CO 2 reduction. The optimized photocatalyst achieves a high CO formation rate of 46.82 μmol g cat −1 with 70.1% selectivity in solid−liquid mode without sacrificial agents, which is 2.68 and 2.18-fold compared to that of exclusive silver single-atom (Ag 1 − CN) and cobalt−silver dual-metal site (Co 1 Ag 1 −PCN) photocatalysts, respectively. The closely integrated in situ experiments and density functional theory calculations unravel that the electronic metal−support interactions (EMSIs) of Ag nanoparticles with adjacent Ag−N 2 C 2 and Co−N 6 −P single-atom sites promote the adsorption of CO 2 * and COOH* intermediates to form CO and CH 4 , as well as boost the enrichment and transfer of photoexcited electrons. Moreover, the atomically dispersed dual-metal Co−Ag SA sites serve as the fast-electrontransfer channel while Ag nanoparticles act as the electron acceptor to enrich and separate more photogenerated electrons. This work provides a general platform to delicately design high-performance synergistic catalysts for highly efficient solar energy conversion.

Anchoring of NiCox alloy nanoparticles on nitrogen vacancy-rich carbon nitride nanotubes toward promoting efficiently photocatalytic CO2 conversion into solar fuel

“…33 The CH 4 evolution rate and selectivity over NiCo 0.4 /V N -CNNTs ranks in the forefront in comparison with the previously reported C 3 N 4 -based photocatalysts, as listed in Fig. 5b and Table S1 † 29,32,52,57–61 . This demonstrates that the decoration of non-noble alloys is an effective strategy for C 3 N 4 -based photocatalysts to produce high value-added CH 4 in solar-driving conversion of CO 2 .…”

Dual-atom-site Cu@PCN photocatalyst selectively produces ethane from CO2 reduction

“…However, structural controlling of active sites is still a challenge in the manufacture of most bimetallic atomic catalysts, because atoms inevitably reunite to form clusters during the preparation of DAS, which will undoubtedly reduce the total amount of bimetallic dimers. 12–15 Moreover, the deviation distance between the two atoms of the dimer, as well as the existence of different configurations, would also limit the synergistic effect and then decrease the catalytic activity. 16–19 The employment of precursors has been an effective strategy for the preparation of catalysts, and dual-copper precursors with an atom precise structure can exactly locate the catalytic copper sites, preventing particles with excessive size from atomic aggregation due to low catalytic activity.…”

Photochemical Tuning of Tricoordinated Nitrogen Deficiency in Carbon Nitride to Create Delocalized π Electron Clouds for Efficient CO2 Photoreduction

“…Graphitic carbon nitride (g-C 3 N 4 ) emerges as an ideal metal-free semiconductor for driving CO 2 reduction in various studies, − characterized by two-dimensional (2D) frameworks of tri-s-triazine (heptazine) bridged by tertiary amines. Owing to its 2D conjugated configurations, g-C 3 N 4 presents unique electronic structures and high thermochemical stability, along with eco-friendly and earth-abundant features and facile preparation, making it a promising candidate for CO 2 PR.…”