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

Abstract

Conspectus Syngas conversion is a key platform for efficient utilization of various carbon-containing resources including coal, natural gas, biomass, organic wastes, and even CO2. 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 Co0 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 (Co2C) phase is typically viewed as an undesirable compound that could lead to deactivation with low activity and high methane selectivity. Although iron carbide (Fe x C) 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 Co2C 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 Co2C 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 Co2C 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 Co2C, the promotional effect of alkali and Mn promoters, and the role of metal–support interaction (SMI) in fabricating supported Co2C nanoprisms. Specially, we briefly review the synthetic methods for different Co2C nanostructures. In addition, Co2C can also be applied as a nondissociative adsorption center for higher alcohol synthesis (HAS) via syngas conversion. We also discuss the construction of a Co0/Co2C 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 Co2C nanocatalysts described here present a critic step to produce chemicals through the FTS process.

Advances in Selectivity Control for Fischer–Tropsch Synthesis to Fuels and Chemicals with High Carbon Efficiency

“…Significant advances have been achieved to break the restriction of the ASF distribution and maximize the selectivity of specific target products while minimizing undesired C1 byproducts by developing efficient catalysts and a process intensification strategy. ,, For example, the integration of a Fischer–Tropsch (FT) metal and zeolite can realize the cascade reaction to directly produce middle-distillate hydrocarbon fuels with very high selectivity (>60%) from syngas . Modified Fe-based catalyst and cobalt carbide have been reported to generate the theoretically achievable extreme value of lower olefins (∼60%) with a negative deviation of the ASF distribution for methane. − We herein will mainly review recent advances in designing heterogeneous catalysts for selectivity control of FTS to hydrocarbon fuels and chemicals, especially for olefins, aromatics, and higher alcohols. The inspiring catalytic performance, novel catalytic active site structure, and underlying reaction mechanism will be involved.…”

Direct production of olefins from syngas with ultrahigh carbon efficiency

“…The classic Fischer-Tropsch synthesis (FTS) process mainly produces heavy saturated hydrocarbons over a variety of metal catalysts including iron, cobalt, and ruthenium 12 . To date, only promoted iron- or cobalt carbide catalysts can effectively catalyze FTO reaction with selectivity to lower olefins in hydrocarbons up to 60% 9 , 13 , 14 . Nevertheless, both OX-ZEO and metal carbide-based FTO processes commonly exhibit high selectivity to CO 2 by-products in the range of 30%~50%, significantly decreasing the carbon utilization efficiency 7 , 11 , 15 , 16 .…”

A Monodisperse ε′-(CoxFe1–x)2.2C Bimetallic Carbide Catalyst for Direct Conversion of Syngas to Higher Alcohols

“…Syngas (CO + H 2 ) is one of the most important C1-chemistry platforms for the conversion of various carbon-containing sources (coal, natural gas, and biomass) to synthesis fuels and value-added chemicals such as alcohols and olefins. − Higher alcohols (HA), containing two or more carbons, can be applied as clean fuels, gasoline additives, feedstocks and intermediates for the production of fine chemicals . Great efforts have been made to developing catalysts for higher alcohol synthesis (HAS) from syngas.…”