Inducing synergy in bimetallic RhNi catalysts for CO2 methanation by galvanic replacement

CO2 reduction by H2 on heterogeneous catalysts is an important class of reactions that has been studied for decades. However, atomic scale details of structure-function relationships are still poorly understood. Particularly, it has been suggested that metal particle size plays a unique role in controlling the stability of CO2 hydrogenation catalysts and the distribution of active sites, which dictates reactivity and selectivity. These studies often have not considered the possible role of isolated metal active sites in the observed dependences. Here, we utilize probe molecule diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with known site-specific extinction coefficients to quantify the fraction of Rh sites residing as atomically dispersed isolated sites (Rhiso), as well as Rh sites on the surface of Rh nanoparticles (RhNP) for a series of TiO2 supported Rh catalysts. Strong correlations were observed between the catalytic reverse water gas shift turn over frequency (TOF) and the fraction of Rhiso sites and between catalytic methanation TOF and the fraction of RhNP sites. Furthermore, it was observed that reaction condition-induced disintegration of Rh nanoparticles, forming Rhiso active sites, controls the changing reactivity with time on stream. This work demonstrates that isolated atoms and nanoparticles of the same metal on the same support can exhibit uniquely different catalytic selectivity in competing parallel reaction pathways and that disintegration of nanoparticles under reaction conditions can play a significant role in controlling stability.

This tutorial review, of relevance for the surface science and heterogeneous catalysis communities, provides a molecular-level discussion of the nature of the active sites in metal catalysis. Fundamental concepts such as "Brønsted-Evans-Polanyi relations" and "volcano curves" are introduced, and are used to establish a strict partitioning between the so-called "electronic" and "geometrical" effects. This partitioning is subsequently employed as the basis for defining the concept "degree of structure sensitivity" which can be used when analyzing the structure sensitivity of catalytic reactions.

CO 2 hydrogenation to hydrocarbons is a promising way of making waste to wealth and energy storage, which also solves the environmental and energy issues caused by CO 2 emissions. Much efforts and research are aimed at the conversion of CO 2 via hydrogenation to various value-added hydrocarbons, such as CH 4 , lower olefins, gasoline, or long-chain hydrocarbons catalyzed by different catalysts with various mechanisms. This review provides an overview of advances in CO 2 hydrogenation to hydrocarbons that have been achieved recently in terms of catalyst design, catalytic performance and reaction mechanism from both experiments and density functional theory calculations. In addition, the factors influencing the performance of catalysts and the first C–C coupling mechanism through different routes are also revealed. The fundamental factor for product selectivity is the surface H/C ratio adjusted by active metals, supports and promoters. Furthermore, the technical and application challenges of CO 2 conversion into useful fuels/chemicals are also summarized. To meet these challenges, future research directions are proposed in this review. CO 2 hydrogenation to hydrocarbons over heterogeneous catalysts.