Cobalt Carbide Nanocatalysts for Efficient Syngas Conversion to Value-Added Chemicals with High Selectivity.

Syngas conversion is a key platform for efficient utilization of various carbon-containing resources including coal, natural gas, biomass, organic wastes, and even CO. One of the most classic routes for syngas conversion is Fischer-Tropsch synthesis (FTS), which is already available for commercial application. However, it still remains a grand challenge to tune the product distribution from paraffins to value-added chemicals such as olefins and higher alcohols. Breaking the selectivity limitation of the Anderson-Schulz-Flory (ASF) distribution has been one of the hottest topics in syngas chemistry.Metallic Co is a well-known active phase for Co-catalyzed FTS, and the products are dominated by paraffins with a small amount of chemicals (i.e., olefins or alcohols). Specifically, a cobalt carbide (CoC) phase is typically viewed as an undesirable compound that could lead to deactivation with low activity and high methane selectivity. Although iron carbide (FeC) can produce olefins with selectivity up to ∼60%, the fraction of methane is still rather high, and the required high reaction temperature (300-350 °C) typically causes coke deposition and fast deactivation. Recently, we discovered that CoC nanoprisms with preferentially exposed facets of (020) and (101) can effectively produce olefins from syngas conversion under mild reaction conditions with high selectivity. The methane fraction was limited within 5%, and the product distribution deviated greatly from ASF statistic law. The catalytic performances of CoC nanoprisms are completely different from that reported for the traditional FT process, exhibiting promising potential industrial application.This Account summarizes our progress in the development of CoC nanoprisms for Fischer-Tropsch synthesis to olefins (FTO) with remarkable efficiencies and stability. The underlying mechanism for the observed unique catalytic behaviors was extensively explored by combining DFT calculation, kinetic measurements, and various spectroscopic and microscopic investigation. We also emphasize the following issues: particle size effect of CoC, the promotional effect of alkali and Mn promoters, and the role of metal-support interaction (SMI) in fabricating supported CoC nanoprisms. Specially, we briefly review the synthetic methods for different CoC nanostructures. In addition, CoC can also be applied as a nondissociative adsorption center for higher alcohol synthesis (HAS) via syngas conversion. We also discuss the construction of a Co/CoC interfacial catalyst for HAS and demonstrate how to tune the reaction network and strengthen CO nondissociative adsorption ability for efficient production of higher alcohols. We believe that the advances in the development of CoC nanocatalysts described here present a critic step to produce chemicals through the FTS process.