Design and synthesis of high-performance heterogeneous catalysts are of immense interest in chemical industries. Herein, ultrafine H 2 O coordinated WO x nanoparticles (H 2 O−WO x , average diameter 2.24 nm) embedded into porous carbon matrix have been obtained via spaceconfinement pyrolysis with postmodification oxidation approach. The synthesized H 2 O−WO x nanoparticles exhibit high activities toward olefin epoxidation reaction using H 2 O 2 as oxidant. In epoxidation of cis-cyclooctene, the turnover frequency of the catalyst can achieve as high as 949 h −1 , an activity comparable to the highest of all reported early transition-metal based catalysts. UV−vis spectra and controlled catalytic experiments have been performed to ascertain the possible active site in the catalyst: compared with traditional WO 3 and peroxide coordinated W-(η 2 -O 2 ) species, the water coordinated H 2 O−WO x can transform to hydroperoxide HOO−WO x in the presence of H 2 O 2 , and the HOO−WO x species can be further activated by proton acid to enhance its catalytic activities.

Design and synthesis of efficient small organic molecule-based electrooxidation catalysts in replacing conventional oxygen evolution reaction (OER) catalysts has been considered as an alternative path to enable largescale renewable energy storage. In contrast to OER, alcohol oxidation reactions can be implemented at lower applied potentials along with generating higher value-added byproducts than oxygen. Here, the ultrafine Ni/WC hybrid nanoparticles (NPs) were successfully synthesized via an in situ trapping and space-confinement pyrolysis strategy. The as-synthesized Ni/WC hybrid NPs exhibit high electrooxidation performances in oxidizing methanol, ethanol, iso-propanol, ethylene glycol, and propylene glycol in alkaline solution. Particularly, for the methanol oxidation reaction, Ni/WC NPs demonstrate high reaction activity (specific activity: 325 mA cm −2 at 0.6 V vs Ag/AgCl/3.5 M KCl; mass activity: 1363 mA mg −1 ) and excellent stability (catalytic current drops ∼6.8% after 4 h). In the first 6 h of the electrolysis process, methanol was effectively converted into formate with ca. 93.8% Faraday efficiency. Based on in situ IR spectra and control catalyst experiments, tungsten carbide (WC) and nickel oxyhydroxide (NiOOH, derived from Ni) species are capable of activating different functional groups of methanol. More interestingly, their hybrid structure (Ni/WC) demonstrates improved catalytic performance in converting methanol into a formate product for the synergistic effect.

A manganese(iii,iv)-tungsten(vi) supercluster based on 72 manganese ions (48 MnIV and 24 MnIII) and 48 tungsten(vi) centers [{MnIV24MnIII12O28(H2O)23}2(W24O120)2]40- has been prepared from the carboxylic Mn12 cluster. Its structure comprises two unprecedented cage-like Mn36W24 cores linked via two Mn-O-W bonds, leading to a Mn72W48 assembly. The inorganic synthetic mechanism was investigated through different synthesis methods and comprehensive ESI-MS tests.

A high-nuclear Mn 72 W 48 cluster has been successfully synthesized by employing acetate coordinated Mn12 and Na2WO4 as starting materials. To investigate the synthesis mechanism, a series of synthesis experiments and high-resolution ESI-MS tests were designed and conducted. These experimental results demonstrate that inorganic tungstates exhibit better coordination capacity and variability than organic acetates in Mn 12 . Furthermore, a series of low nuclearity Mn clusters and Mn–W species were successfully detected and a possible synthesis mechanism of Mn 72 W 48 was proposed. These results show that inorganic tungstate ligands have a great potential to construct high-nuclear transition-metal-oxo clusters by forming various intermediates.