This review evaluates data on catalyst development for thermocatalytic decomposition of methane. We present correlations between catalyst characteristics, catalytic activity (TOF), and catalyst stability (TON), notably for mono-metallic nickel and iron catalysts, which show a correlation between metal particle size and catalyst activity and stability.

Abstract

Thermocatalytic decomposition of methane provides opportunities for hydrogen (H₂) production with no emission of carbon dioxide. However, high-value carbon products need to be produced for economic deployment of thermocatalytic decomposition and to achieve a minimum H₂ selling price below the U.S, Department of Energy target of $ 1/kg H₂. In this review, we re-evaluate data on catalyst development reported in the literature and propose correlations between catalyst characteristics, catalytic stability, and properties of carbon co-products. In the first part of the review, growth mechanisms for carbon nanotubes using state-of-the-art chemical vapor deposition are reviewed to catalog the effects of catalyst characteristics, the influence of carbon sources, interactions between metal particles and supports, and metal particle sizes on carbon growth. In the second part, representative developments in mono-, bi-, and tri-metallic nickel catalysts are highlighted. We present kinetic analysis of reactions catalyzed by mono-metallic nickel catalysts, which generates a correlation between metal particle size and catalyst stability. Rational design of Ni-based catalysts for TCD of methane requires attention to the size of the metal particle and effective normalization of the reaction rates. Further attention to the distribution of the metal particle sizes may help identify catalyst properties that contribute longevity and selectivity to processes that use them. While it is tempting to focus on the highest valued carbon products (e. g., CNTs and CFs), analysis of the markets for other carbon products suggests that a more flexible approach may generate comparable returns without the risk associated with specialization.