Direct conversion of methane to chemical feedstocks such as methanol under mild conditions is a challenging but ideal solution for utilization of methane. Pd O single-sites anchored on the internal surface of micropores of a microporous silicate exhibit high selectivity and activity in transforming CH to CH OH at 50-95 °C in aqueous phase through partial oxidation of CH with H O . The selectivity for methanol production remains at 86.4 %, while the activity for methanol production at 95 °C is about 2.78 molecules per Pd O site per second when 2.0 wt % CuO is used as a co-catalyst with the Pd O @ZSM-5. Thermodynamic calculations suggest that the reaction toward methanol production is highly favorable compared to formation of a byproduct, methyl peroxide.

A copper-doped porous metal oxide catalyst in combination with hydrogen shows selective and quantitative hydrogenolysis of benzyl ketones and aldehydes, and hydrogenation of alkenes.

Direct conversion of methane to chemical feedstocks such as methanol under mild conditions is a challenging but ideal solution for utilization of methane. Pd1O4 single‐sites anchored on the internal surface of micropores of a microporous silicate exhibit high selectivity and activity in transforming CH4 to CH3OH at 50–95 °C in aqueous phase through partial oxidation of CH4 with H2O2. The selectivity for methanol production remains at 86.4 %, while the activity for methanol production at 95 °C is about 2.78 molecules per Pd1O4 site per second when 2.0 wt % CuO is used as a co‐catalyst with the Pd1O4@ZSM‐5. Thermodynamic calculations suggest that the reaction toward methanol production is highly favorable compared to formation of a byproduct, methyl peroxide.

Designing effective and selective reactions at sustainable or mild conditions is key for the valorization or refinery of lignin biomass using H2 reduction methods. However, it remains unclear what are the feasible mildest conditions for the reductive valorization of lignin, at which transformations can be designed. Here, we aim to exploit this critically important question using quantum chemistry calculations to systematically analyze the thermodynamics of hydrogenation and hydrogenolysis of typical functional groups found in lignin based on a set of aromatic model compounds. Our results show that it is thermodynamically feasible to break ether linkages and remove oxygen content in the model compounds even at room temperature, room pressure, and in aqueous solvent (i.e., the global mildest conditions). Interestingly, the potential influence on the thermodynamics by reaction variables is ranked in the order of temperature > H2 pressure > solvent dielectric constant; a strategically chosen solvent may enable increased selectivity for hydrogenolysis over hydrogenation. Our predicted reaction thermodynamics is consistent with our experimental findings of probed reaction pathways. This work may inspire researchers to pursue the design of “ultimate” green biomass conversion processes closer to the global mildest conditions.