Single atom (SA) catalysts have achieved great success on highly selective heterogeneous catalysis due to their abundant and homogeneous active sites. The electronic structures of these active sites, restrained by their localized coordination environments, significantly determine their catalytic performances, which are difficult to manipulate. Here, we investigated the effect of localized surface plasmon resonance (LSPR) on engineering the electronic structures of single atomic sites. Typically, core–shell structures consisted of Au core and transition metal SAs loaded N-doped carbon (CN) shell were constructed, namely Au@M-SA/CN (M = Ni, Fe, and Co). It was demonstrated that plasmon-induced hot electrons originated from Au were directionally injected to the M-SAs under visible light irradiation, which significantly changed their electronic structures and meanwhile facilitated improved overall charge separation efficiency. The as-prepared Au@Ni-SA/CN exhibited highly efficient and selective photocatalytic CO₂ reduction to CO performance, which is 20.8, 17.5, and 6.9 times those of Au nanoparticles, Au@CN, and Ni-SA/CN, respectively. Complementary spectroscopy analysis and theoretical calculations confirmed that the plasmon enhanced Ni-SA/CN sites featured increased charge density for efficient intermediate activation, contributing to the superb photocatalytic performance. The work provides a new insight on plasmon and atomic site engineering for efficient and selective catalysis.

The semiconductor-based photoanodes have shown great potential on photoelectrochemical (PEC) hydrogen generation. Compared to the pristine semiconductor, photoanodes fabricated with doped semiconductors exhibit modulated bandgap structure and enhanced charge separation efficiency, demonstrating improved optoelectronic properties. In this work, we develop a colloidal cation exchange (CE) strategy on versatile synthesis of heterovalent doped chalcogenide semiconductor thin films with high surface roughness. Using Ag-doped CdSe (CdSe:Ag) thin films as an example, the organized centimeter-scale CdSe:Ag films with nanometer-scale thickness (thickness around 80 nm, length × width around 1.5 cm × 1.2 cm) exhibit enhanced optical absorbance ability and charge carrier density by tuning the energy levels of conduction and valence bands as well as improved electrical conductivity by Ag dopants compared to the pristine CdSe film obtained by the vapor-phase vacuum deposition strategy. In the meantime, the surface roughness of the as-prepared semiconductor thin films is also increased with abundantly exposed active sites to facilitate accessibility to water for hydrogen generation and suppress photogenerated carrier recombination. The CdSe:Ag film photoanodes exhibit superb PEC hydrogen generation performance with a photocurrent density of 0.56 mA/cm² at 1.23 V versus reversible hydrogen electrode, which is nearly 3 times higher than the pristine CdSe film. This work provides a new strategy on colloidal synthesis of photoelectrodes with modulated heterovalent doping and surface roughness for PEC applications.

Electronic doped quantum dots (Ed-QDs), by heterovalent cations doping, have held promise for future device concepts in optoelectronic and spin-based technologies due to their broadband Stokes-shifted luminescence, enhanced electrical transport and tailored magnetic behavior. Considering their scale-up requirement and the low yielding of several current colloidal synthesis methods, a stable and efficient bulk synthesis strategy must be developed. Microreactors have long been recognized as an effective platform for producing nanomaterials and fabricating large-scale structures. Here, we chose microreactor platform for continuous synthesis of Ed-QDs in the air at low temperatures. By original reverse cation exchange reaction mechanism together with varying the kinetic conditions of microreactor platform, such as liquid flow rate, the Ag doped CdS (CdS:Ag) Ed-QDs with higher yield have been synthesized successfully due to the continuous synthesis advantages with a high degree of size selectivity. Enabled by microreactor engineering simulation, this research not only provides a new synthetic method towards scale-up production but also enables to improve chemical mass production of similar functional QDs for optical devices, bio-imaging and innovative information processing applications.