Near-infrared-featured broadband CO2 reduction with water to hydrocarbons by surface plasmon

Abstract

Imitating the natural photosynthesis to synthesize hydrocarbon fuels represents a viable strategy for solar-to-chemical energy conversion, where utilizing low-energy photons, especially near-infrared photons, has been the ultimate yet challenging aim to further improving conversion efficiency. Plasmonic metals have proven their ability in absorbing low-energy photons, however, it remains an obstacle in effectively coupling this energy into reactant molecules. Here we report the broadband plasmon-induced CO2 reduction reaction with water, which achieves a CH4 production rate of 0.55 mmol g−1 h−1 with 100% selectivity to hydrocarbon products under 400 mW cm−2 full-spectrum light illumination and an apparent quantum efficiency of 0.38% at 800 nm illumination. We find that the enhanced local electric field plays an irreplaceable role in efficient multiphoton absorption and selective energy transfer for such an excellent light-driven catalytic performance. This work paves the way to the technique for low-energy photon utilization.

Active Site Engineering on Plasmonic Nanostructures for Efficient Photocatalysis

“…Moreover, the formed CO bound strongly to the Cu sites to experience further hydrogenation for CH 4 production. Most recently, Hu et al reported the Au rod@CuPd 2 core–shell composite for broadband CO 2 reduction with H 2 O (Figure g) . It was reported that the Au plasmon-induced local electric field facilitated i) the formation of quasi isolated trap states above the Fermi level of the hybrid state between CO 2 and CuPd (extending the lifetime of hot carriers) and ii) the selective energy transfer to CO 2 than H 2 O (limiting the competitive H 2 production reaction).…”

“…Most recently, Hu et al reported the Au rod@CuPd 2 core−shell composite for broadband CO 2 reduction with H 2 O (Figure 13g). 11 It was reported that the Au plasmon-induced local electric field facilitated i) the formation of quasi isolated trap states above the Fermi level of the hybrid state between CO 2 and CuPd (extending the lifetime of hot carriers) and ii) the selective energy transfer to CO 2 than H 2 O (limiting the competitive H 2 production reaction). In addition, a spherical reactor design for gas−solid phase CO 2 reduction was proposed to enable the reincidence of scattered photons, leading to high photon utilization efficiency.…”

“…The rational design and preparation of active sites on plasmonic nanostructures hold a prerequisite for plasmonic photocatalysis-related research. A central concept of active site engineering is to enhance the adsorption (especially chemisorption) of reactants on the catalyst surface, allowing efficient orbital hybridization and energy coupling between plasmonic photocatalysts and surface reactants. , In the past ten years, numerous active site-engineered plasmonic nanostructures have been developed for the photocatalytic conversion of various reactants. ,− Although the requirements on active sites can differ from different reactions, the methods for preparing active site-engineered plasmonic nanostructures can still be referable.…”

“…Right panel: average CH 4 production rates obtained for gas–solid phase CO 2 reduction over Au rod@CuPd 2 . Reproduced with permission under a Creative Commons CC BY license from ref . Copyright 2023 The Authors.…”

“…Through photocatalysis, solar energy can be directly harvested and coupled into catalytic reactions for chemical transformation, substantially lowering the energy demands for high temperatures or other harsh conditions. In this sense, a well-designed photocatalytic system that efficiently utilizes solar energy will be highly desirable for realizing sustainable chemical manufacturing. − …”