Chlorohydrins are essential intermediates in organic synthesis, playing a critical role in drug discovery, green catalysis, and bioactive molecule manufacturing. However, conventional chlorohydrin synthesis usually requires harsh conditions, which create safety risks and poor selectivity. Here we develop a direct and efficient electrocatalytic strategy for synthesizing chlorohydrins from commodity alkenes, which are globally produced at over 200 million metric tons annually. Utilizing a RuSnNbOx polymetallic oxide catalyst, cyclohexene is directly converted to 2-chlorocyclohexanol in NaCl solution with a Faradaic efficiency of 96.1 ± 3% and selectivity of 98.2 ± 0.4% at 1.6 V versus reversible hydrogen electrode. This approach is generalizable to other alkenes, such as styrene and cyclopentene, yielding 2-chloro-1-phenylethanol and 2-chlorocyclopentanol with uncompromised Faradaic efficiency. Mechanistic investigations reveal that the adsorbed active chlorine species, electrogenerated via Cl− oxidation on the RuSnNbOx anode, serve as key intermediates for direct alkene chlorination. Notably, this electrosynthesis method is further upscaled to gram-level in acidic seawater, delivering 3.01 g of 2-chlorocyclohexanol and 0.87 g of 2-chloro-1-phenylethanol. This work provides a sustainable and scalable alternative to conventional chlorohydrin production and offers insights into designing efficient electrolysis for related transformations.

Electrocatalytic conversion of CO2 to ethylene (C2H4), the cornerstone of the chemical industry, offers a sustainable alternative to conventional energy-intensive steam cracking but remains limited by inefficient C-C coupling and competing hydrogen evolution reaction. Here, we report an organic-inorganic grain-boundary (OIGB) catalyst by embedding CuO nanodomains within a Cu-based metal-organic framework matrix, which creates well-defined electronically integrated interfaces that enable cooperative stabilization of *CO and *COH intermediates. The OIGB structure achieves a high Faradaic efficiency of ∼81% for CO2 electroreduction to C2H4 at an industrially relevant current density of 300 mA cm−2, together with stable operation for over 100 h. Operando spectroscopy combined with computational calculations reveals a synergistic mechanism in which CuO nanodomains serve as local *CO generation sites while Cu–N coordination sites stabilize *COH species, associated with formation of the key *COH-CO intermediate for CO2 electroreduction to C2H4.

The oxygen evolution reaction (OER) is a pivotal process in electrochemical energy conversion. Herein, we report a computational study-guided experimental work that uncovers the dynamics of active sites in a heterostructure composed of two distinct phases: Brunogeierite (Fe2GeO4) and serpentine (Ni3Ge2O5(OH)4). This heterostructure is synthesized by introducing varying amounts of a nickel precursor into pristine Fe2GeO4. When comparing pristine materials, Fe in Fe2GeO4 is better for OER as compared with the Ni in Ni3Ge2O5(OH)4. Interestingly, the Ni becomes more active in the heterostructure following the structural distortion and the induced increased electron transfer, which we proved by ex situ/in situ XAS studies. These findings highlight the dynamic evolution of active sites in the heterostructure, elucidating how the synergy between structural and electronic factors transforms catalytic behavior. The optimized heterostructure as an ideal model reveals enhanced electrocatalytic performance with an overpotential of 325 mV versus RHE to achieve a current density of 100 mA cm–2, a Tafel slope of 42 mV dec–1, and long-term stability exceeding 50 h even at high current densities, making it highly promising for a wide range of critical electrolysis applications.