MgO has specific catalysis for CH₄-to-C conversion, and functions as a cost-effective and environmentally friendly template to produce graphene mesosponge with developed porosity, excellent stability, and super soft and elastic properties.

Realizing accurate control of catalytically active centers on solid surfaces is one of the most essential goals in the development of functionalized heterogeneous catalysts. Controlled synthesis of carbon-supported Co catalysts from single-site to nanoparticles can be successfully achieved by the structural transformation of the deposited Co(salen) complex precursor under heat treatment. The obtained structures were characterized using techniques such as XRD, in situ XAFS, and TEM. The first decomposition of the Co(salen) complex is initiated by the dissociation of Co–O–C bonds at around 250 °C, which produces isolated single-atom Co species while retaining the Co–N–C bonds even up to 400 °C. When the heat treatment temperature exceeds 450 °C, the second decomposition of the Co–N–C bonds occurs to form Co oxide nanoclusters followed by the growth of Co NPs upon further increase of the heat treatment temperature. The single-site catalyst is highly dispersed and electronically deficient owing to the interaction with the carbon support, and shows activity and selectivity for the oxidation of ethylbenzene, as compared to the inherent Co(salen) complex and nanoparticle catalysts.

Pd–Co bimetallic catalysts were prepared by the controlled synthesis of carbon-supported Co catalysts, ranging from single-sites to nanoparticles, via structural transformation of a deposited Co(salen) complex precursor by heat treatment at different temperatures, followed by galvanic replacement with Pd ions. The catalysts were structurally characterized using XRD, TEM, HAADF-STEM, XAFS and XPS. Highly dispersed Pd-rich NPs containing a low concentration of Co species were formed and the original size of the Co NPs was retained. The electronic state of the Pd species was dependent on the size of the bimetallic NPs, and a catalyst with a mean diameter of 10.8 nm was found to be in the most electron-rich state. Not only the particle size, but also the electronic state of Pd play a crucial role in attaining high catalytic activity and selectivity in the selective hydrogenation of phenylacetylene. A Pd–Co catalyst based on a Co catalyst heat-treated at 600 °C showed 92% selectivity at 93% conversion. Furthermore, the Pd–Co catalysts synthesized by the galvanic replacement method showed superior performance to a monometallic Pd catalyst and a Pd–Co alloy catalyst.

The structural evolution of highly mesoporous templated carbons is examined from temperatures of 1173 to 2873 K to elucidate the optimal conditions for facilitating graphene-zipping reactions whilst minimizing graphene stacking processes. Mesoporous carbons comprising a few-layer graphene wall display excellent thermal stability up to 2073 K coupled with a nanoporous structure and three-dimensional framework. Nevertheless, advanced temperature-programmed desorption (TPD), X-ray diffraction, and Raman spectroscopy show graphene-zipping reactions occur at temperatures between 1173 and 1873 K. TPD analysis estimates zipping reactions lead to a 1100 fold increase in the average graphene-domain, affording the structure a superior chemical stability, electrochemical stability, and electrical conductivity, while increasing the bulk modulus of the framework. At above 2073 K, the carbon framework shows a loss of porosity due to the development of graphene-stacking structures. Thus, a temperature range between 1873 and 2073 K is preferable to balance the developed graphene domain size and high porosity. Utilizing a neutron pair distribution function and soft X-ray emission spectra, we prove that these highly mesoporous carbons already consist of a well-developed sp²-carbon network, and the property evolution is governed by the changes in the edge sites and stacked structures.