Effective desorption of chlorine species is critical for hindering the formation of chlorinated intermediates in the catalytic destruction of chlorinated volatile organic compounds (CVOCs). Here, Ru/MnCo3O x catalysts with excellent activity, reaction durability and superior chlorine transformation ability for 1,2-dichloroethane (1,2-DCE) destruction were rationally fabricated. The presence of Ru facilitates the electron transfer among Ru, Mn, Co, and O species, forming larger amounts of Ru6+/Ru4+, Mn4+, Co2+, and active oxygen species (O2–), and therefore promoting the catalytic activity via accelerating and strengthening the cleavage of the C–Cl bond at low temperatures. However, Ru species plays a neutral role in the desorption of surface chlorine species under dry conditions and the polychlorinated byproducts such as CH2Cl2, CHCl3, CCl4, CH2ClCHCl2, and CHClCCl2 are inevitably formed. Interestingly, the desorption of chlorine species over Ru-based catalysts can be dramatically promoted under humid conditions, suppressing the formation of hazardous polychlorinated byproducts effectively (over 3 times lower under 2 vol % of water vapor conditions than the dry conditions). Results reveal that the presence of Ru enables Cl species transformation and dissociation over the catalyst surface that fosters the destruction of 1,2-DCE on adjacent Mn/Co sites under humid conditions, providing a rationale for high catalytic activity of the catalysts and paving the way for industrially relevant CVOC benign destruction.

Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non‐metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. Here, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru3O2) on reduced graphene oxide (rGO), attributed to the suppression of diffusion‐induced metal cluster aggregation. Ru3O2/rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4‐tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO2 nanoparticles, and homogeneous single/multiple‐site Ru catalysts. In addition, Ru3O2/rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru3O2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru3O2 cluster for hydrogen abstraction.

Liquid methanol has the potential to be the hydrogen energy carrier and storage medium for the future green economy. However, there are still many challenges before zero-emission, affordable molecular H 2 can be extracted from methanol with high performance. Here, we present noble-metal-free Cu–WC/W plasmonic nanohybrids which exhibit unsurpassed solar H 2 extraction efficiency from pure methanol of 2,176.7 µmol g −1  h −1 at room temperature and normal pressure. Macro-to-micro experiments and simulations unveil that local reaction microenvironments are generated by the coperturbation of WC/W’s lattice strain and infrared-plasmonic electric field. It enables spontaneous but selective zero-emission reaction pathways. Such microenvironments are found to be highly cooperative with solar-broadband-plasmon-excited charge carriers flowing from Cu to WC surfaces for efficient stable CH 3 OH plasmonic reforming with C 3 -dominated liquid products and 100% selective gaseous H 2 . Such high efficiency, without any CO x emission, can be sustained for over a thousand-hour operation without obvious degradation.

The chemoselective hydrogenation of nitro compounds is limited by a trade-off between the activity and selectivity of catalysis. It is found that MoS2-based catalysts can replace noble metals to achieve nearly 100% selectivity toward hydrogenation to aromatic amines. However, the insufficient supply of active hydrogen (Ha) limits the conversion to a low level. To break the trade-off between activity and selectivity, a dual-active site catalyst was designed using exfoliated MoS2 as a support and modifying it with single-atom Pt as independent, active hydrogen-donating sites. Isolated Pt atoms continuously provide Ha to the hydrogenation sites of MoS2. This strategy solves the problem of insufficient Ha supply, which is caused by the competitive adsorption of nitro groups and hydrogen on MoS2, by matching the rate of Ha production and Ha consumption, resulting in a greatly increased reaction rate.