Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV.

Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.9%. The superior catalytic performance can be attributed to a cooperative effect between the highly dispersed sub-nanometric Pd clusters for hydrogen activation and unique surface sites of PN-CeO2 with a high concentration of oxygen vacancy for an energetically and geometrically preferential adsorption of nitroarenes via nitro group. The high concentration of surface defects of PN-CeO2 and large Pd dispersion contribute to the enhanced catalytic activity for the hydrogenation reactions. The high chemoselectivity is mainly governed by the high Pd dispersion on the support. The catalysts also deliver high catalytic activity and selectivity for nitroaromatics with various reducible substituents into the corresponding aminoarenes.

Unique ethylene glycol ligand environments are utilized to overcome the HER kinetic limitation of CoP modified by a low Pt loading via local proton concentration and subsequent hydrogen spillover.

Searching the high‐efficient, stable, and earth‐abundant electrocatalysts to replace the precious noble metals holds the promise for practical utilizations of hydrogen and oxygen evolution reactions (HER and OER). Here, a series of highly active and robust Co‐doped nickel phosphides (Ni2−xCoxP) catalysts and their hybrids with reduced graphene oxide (rGO) are developed as bifunctional catalysts for both HER and OER. The Co‐doping in Ni2P and their hybridization with rGO effectively regulate the catalytic activity of the surface active sites, accelerate the charge transfer, and boost their superior catalytic activity. Density functional theory calculations show that the Co‐doped catalysts deliver the moderate trapping of atomic hydrogen and facile desorption of the generated H2 due to the H‐poisoned surface active sites of Ni2−xCoxP under the real catalytic process. Electrochemical measurements reveal the high HER efficiency and durability of the NiCoP/rGO hybrids in electrolytes with pH 0–14. Coupled with the remarkable and robust OER activity of the NiCoP/rGO hybrids, the practical utilization of the NiCoP/rGO‖NiCoP/rGO for overall water splitting yields a catalytic current density of 10 mA cm−2 at 1.59 V over 75 h without an obvious degradation and Faradic efficiency of ≈100% in a two‐electrode configuration and 1.0 m KOH.

To search for the efficient non-noble metal based and/or earth-abundant electrocatalysts for overall water-splitting is critical to promote the clean-energy technologies for hydrogen economy. Herein, we report nickel phosphide (NixPy) catalysts with the controllable phases as the efficient bifunctional catalysts for water electrolysis. The phases of NixPy were determined by the temperatures of the solid-phase reaction between the ultrathin Ni(OH)2 plates and NaH2PO2·H2O. The NixPy with the richest Ni5P4 phase synthesized at 325 °C (NixPy-325) delivered efficient and robust catalytic performance for hydrogen evolution reaction (HER) in the electrolytes with a wide pH range. The NixPy-325 catalysts also exhibited a remarkable performance for oxygen evolution reaction (OER) in a strong alkaline electrolyte (1.0 M KOH) due to the formation of surface NiOOH species. Furthermore, the bifunctional NixPy-325 catalysts enabled a highly performed overall water-splitting with ∼100% Faradaic efficiency in 1.0 M KOH electrolyte, in which a low applied external potential of 1.57 V led to a stabilized catalytic current density of 10 mA/cm(2) over 60 h.

Effective activation of CO2 is a prerequisite for efficient utilization of CO2 in organic synthesis. Precisely controlling the interfacial events of solids shows potential for activation. Herein, defect-enriched CeO2 with constructed interfacial frustrated Lewis pairs (FLPs, two adjacent Ce3+···O2–) effectively activates CO2 via the interactions between C/Lewis basic lattice O2– and the two O atoms in CO2/two adjacent Lewis acidic Ce3+ ions. Selective cyclic carbonate production from a catalytically tandem protocol of olefins and CO2 is used to demonstrate FLP-inspired CO2 activation.

Mild oxidation promotes protein network formation and enhances gelation of myofibrillar protein under normal salt and pH conditions used in meat processing. This oxidative effect, which involves disulfide linkages, is somewhat similar to that in bakery product processing where oxidants are used to improve dough performance through gluten protein interaction.

Activation of aryl chlorides for Suzuki−Miyaura coupling (SMC) reactions is particularly challenging for heterogeneous catalysts due to the chemically inert nature of the C−Cl bond. Herein, the multifunctional Pd/Au/ porous nanorods of CeO 2 (PN-CeO 2 ) catalysts with a well-defined spatial configuration deliver the first example of heterogeneous catalysts to activate the strong C−Cl bond under the irradiation of visible light (>400 nm) at room temperature. PN-CeO 2 with strong basicity not only provides the photogenerated electrons to enrich the electron density of metal nanoparticles but also generates holes for activation of arylboronic acids. Meanwhile, due to the strong local surface plasma resonance, the hot electrons from Au nanoparticles excited by visible light can be injected into Pd nanocatalysts that are spatially contacted with Au nanoparticles. Thus, Pd nanocatalysts with significantly enriched electron density efficiently activate the aryl chlorides under the visible light irradiation at room temperature. The high catalytic activity and reusability of multifunctional photocatalysts associated with full use of the photogenerated electrons and holes inspire the future exploitation for the activation of unreactive chemical bonds under mild conditions.