Photocatalytic CO2 reduction (PCR) is able to convert solar energy into chemicals, fuels, and feedstocks, but limited by the deficiencies of photocatalysts in steering photon-to-electron conversion and activating CO2, especially in pure water. Here we report an efficient, pure water CO2-to-CO conversion photocatalyzed by sub-3-nm-thick BiOCl nanosheets with van der Waals gaps (VDWGs) on the two-dimensional facets, a graphene-analog motif distinct from the majority of previously reported nanosheets usually bearing VDWGs on the lateral facets. Compared with bulk BiOCl, the VDWGs-rich atomic layers possess a weaker excitonic confinement power to decrease exciton binding energy from 137 to 36 meV, consequently yielding a 50-fold enhancement in the bulk charge separation efficiency. Moreover, the VDWGs facilitate the formation of VDWG-Bi-VO••-Bi defect, a highly active site to accelerate the CO2-to-CO transformation via the synchronous optimization of CO2 activation, *COOH splitting, and *CO desorption. The improvements in both exciton-to-electron and CO2-to-CO conversions result in a visible light PCR rate of 188.2 μmol g−1 h−1 in pure water without any co-catalysts, hole scavengers, or organic solvents. These results suggest that increasing VDWG exposure is a way for designing high-performance solar-fuel generation systems.

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Seawater is one of the most important CO2 sequestration media for delivering value‐added chemicals/fuels and active chlorine; however, this scenario is plagued by sluggish reaction rates and poor product selectivity. Herein, we first report the synthesis of nitrogen‐doped BiOCl atomic layers to directly split carbon‐sequestrated natural seawater (Yellow Sea, China) into stoichiometric CO (92.8 μmol h−1) and HClO (83.2 μmol h−1) under visible light with selectivities greater than 90 %. Photoelectrons enriched on the exposed BiOCl{001} facet kinetically facilitate CO2‐to‐CO reduction via surface‐doped nitrogen bearing Lewis basicity. Photoholes, mainly located on the lateral facets of van der Waals gaps, promote the selective oxidation of Cl− into HClO. Sequestrated CO2 also maintains the pH of seawater at around 4.2 to prevent the alkaline earth cations from precipitating. The produced HClO can effectively kill typical bacteria in the ballast water of ocean‐going cargo ships, offering a green and safe way for onsite sterilization.

Heavy metals chelated with coexisting organic ligands in wastewater impose severe risks to public health and the ambient ecosystem but are also valuable metal resources. For sustainable development goals, the treatment of heavy metal complexes wastewater requires simultaneous metal–organic bond destruction and metal resource recovery. In this study, we demonstrated that a neutral pH electro-Fenton (EF) system, which was composed of an iron anode, carbon cloth cathode, and sodium tetrapolyphosphate electrolyte (Na6TPP), could induce a successive single-electron activation pathway of molecular oxygen due to the formation of Fe­(II)-TPP complexes. The boosted •OH generation in the Na6TPP-EF process could decomplex 99.9% of copper ethylene diamine tetraacetate within 8 h; meanwhile, the released Cu ions were in situ deposited on the carbon cloth cathode in the form of Cu nanoparticles with a high energy efficiency of 2.45 g kWh–1. Impressively, the recovered Cu nanoparticles were of purity over 95.0%. More importantly, this neutral EF strategy could realize the simultaneous removal of Cu, Ni, and Cr complexes from real electroplating effluents. This study provides a promising neutral EF system for simultaneous heavy metal complexes wastewater treatment and resource recovery and sheds light on the importance of molecular oxygen activation in the field of pollutant control.

The migration and bioavailability of Cr(vi) are determined by its adsorption behavior, which is sensitive to the coordination environment of mineral surfaces, especially natural surface defects, such as surface hydroxyls and oxygen vacancies.