The rational design of functional materials through targeted element-selection strategies offers a promising route for developing next-generation catalysts. Here, we employ this strategy to tackle critical challenges in the Reverse Water Gas Shift (RWGS) reaction, including catalyst deactivation, low CO selectivity, and the high cost of conventional transition-metal catalysts. Through this approach, we designed and synthesized a novel class of metal-free boron-oxy-carbide (BO) catalysts. The catalyst exhibited 100 % CO selectivity and maintained equilibrium CO₂ conversion without deactivation for over 250 h at 600 °C. Advanced characterization techniques, combined with density functional theory (DFT) calculations suggested that the ‘B-O-C triad’ within the BO lattice is responsible for the RWGS activity. These findings demonstrate the potential of BO catalysts as robust, scalable, and sustainable alternatives to state-of-the-art transition-metal-based catalysts for CO₂ valorization. We anticipate that these findings will provide a foundation for the design and activity of metal-free catalysts applicable to a diverse range of chemical transformations.

MXenes are a new family of 2D carbides or nitrides that have attracted attention due to their layered structure, tunable surface groups and high electrical conductivity. Here, we report for the first time that the Ti₂CT_x MXene catalyses the selective oxidative dehydrogenation of n-butane to butenes and 1,3-butadiene. This catalyst showed higher intrinsic activity compared to a commercial TiC and TiO₂ samples in terms of C₄ olefin formation rate. We propose that the stabilisation of structural vacancies and the change in composition (from a carbide to a mixed phase oxide) in the MXene causes its higher catalytic activity. These vacancies can lead to a higher concentration of unpaired electrons in the MXene-derived material, enhancing its nucleophilic properties and favouring the production of olefins.

MAX (Mn+1AXn) phases are layered carbides or nitrides with a high thermal and mechanical bulk stability. Recently, it was shown that their surface structure can be modified to form a thin non-stoichiometric oxide layer, which can catalyze the oxidative dehydrogenation of butane. Here, the use of a Ti2AlC MAX phase as a support for cobalt oxide was explored for the dry reforming of butane with CO2, comparing this new catalyst to more traditional materials. The catalyst was active and selective to synthesis gas. Although the surface structure changed during the reaction, the activity remained stable. Under the same conditions, a titania-supported cobalt oxide catalyst gave low activity and stability due to the agglomeration of cobalt oxide particles. The Co3O4/Al2O3 catalyst was active, but the acidic surface led to a faster deactivation. The less acidic surface of the Ti2AlC was better at inhibiting coke formation. Thanks to their thermal stability and acid-base properties, MAX phases are promising supports for CO2 conversion reactions.