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 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 (FexC) 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.

Cobalt carbide nanoprisms for direct production of lower olefins from syngas.

Lower olefins-generally referring to ethylene, propylene and butylene-are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The 'Fischer-Tropsch to olefins' (FTO) process has long offered a way of producing lower olefins directly from syngas-a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

Control of metal-support interaction for tunable CO hydrogenation performance over Ru/TiO2 nanocatalysts.

The catalytic behavior of CO hydrogenation can be modulated by metal-support interactions, while the role of the support remains elusive. Herein, we demonstrate that the presence of strong metal-support interactions (SMSI) depends strongly on the crystal phase of TiO2 (rutile or anatase) and the treatment conditions for the TiO2 support, which could critically control the activity and selectivity of Ru-based nanocatalysts for CO hydrogenation. High CO conversion and olefin selectivity were observed for Ru/rutile-TiO2 (Ru/r-TiO2), while catalysts supported by anatase (a-TiO2) showed almost no activity. Characterization confirmed that the SMSI effect could be neglected for Ru/r-TiO2, while it is dominant on Ru/a-TiO2 after reduction at 300 °C, resulting in the coverage of Ru nanoparticles by TiOx overlayers. Such SMSI could be suppressed by H2 treatment of the a-TiO2 support and the catalytic activity of the as-obtained Ru/a-TiO2(H2) can be greatly elevated from almost inactive to >50% CO conversion with >60% olefin selectivity. Further results indicated that the surface reducibility of the TiO2 support determines the SMSI state and catalytic performance of Ru/TiO2 in the CO hydrogenation reaction. This work offers an effective strategy to design efficient catalysts for the FTO reaction by regulating the crystal phase of the support.

Engineering ZrO2-Ru interface to boost Fischer-Tropsch synthesis to olefins.

Understanding the structures and reaction mechanisms of interfacial active sites in the Fisher-Tropsch synthesis reaction is highly desirable but challenging. Herein, we show that the ZrO2-Ru interface could be engineered by loading the ZrO2 promoter onto silica-supported Ru nanoparticles (ZrRu/SiO2), achieving 7.6 times higher intrinsic activity and ~45% reduction in the apparent activation energy compared with the unpromoted Ru/SiO2 catalyst. Various characterizations and theoretical calculations reveal that the highly dispersed ZrO2 promoter strongly binds the Ru nanoparticles to form the Zr-O-Ru interfacial structure, which strengthens the hydrogen spillover effect and serves as a reservoir for active H species by forming Zr-OH* species. In particular, the formation of the Zr-O-Ru interface and presence of the hydroxyl species alter the H-assisted CO dissociation route from the formyl (HCO*) pathway to the hydroxy-methylidyne (COH*) pathway, significantly lowering the energy barrier of rate-limiting CO dissociation step and greatly increasing the reactivity. This investigation deepens our understanding of the metal-promoter interaction, and provides an effective strategy to design efficient industrial Fisher-Tropsch synthesis catalysts.

Recent advances in Co2C-based nanocatalysts for direct production of olefins from syngas conversion.

Syngas conversion provides an important platform for efficient utilization of various carbon-containing resources such as coal, natural gas, biomass, solid waste and even CO2. Various value-added fuels and chemicals including paraffins, olefins and alcohols can be directly obtained from syngas conversion via the Fischer-Tropsch Synthesis (FTS) route. However, the product selectivity control still remains a grand challenge for FTS due to the limitation of Anderson-Schulz-Flory (ASF) distribution. Our previous works showed that, under moderate reaction conditions, Co2C nanoprisms with exposed (101) and (020) facets can directly convert syngas to olefins with low methane and high olefin selectivity, breaking the limitation of ASF. The application of Co2C-based nanocatalysts unlocks the potential of the Fischer-Tropsch process for producing olefins. In this feature article, we summarized the recent advances in developing highly efficient Co2C-based nanocatalysts and reaction pathways for direct syngas conversion to olefins via the Fischer-Tropsch to olefin (FTO) reaction. We mainly focused on the following aspects: the formation mechanism of Co2C, nanoeffects of Co2C-based FTO catalysts, morphology control of Co2C nanostructures, and the effects of promoters, supports and reactors on the catalytic performance. From the viewpoint of carbon utilization efficiency, we presented the recent efforts in decreasing the CO2 selectivity for FTO reactions. In addition, the attempt to expand the target products to aromatics by coupling Co2C-based FTO catalysts and H-ZSM-5 zeolites was also made. In the end, future prospects for Co2C-based nanocatalysts for selective syngas conversion were proposed.

Direct production of olefins from syngas with ultrahigh carbon efficiency.

Syngas conversion serves as a competitive strategy to produce olefins chemicals from nonpetroleum resources. However, the goal to achieve desirable olefins selectivity with limited undesired C1 by-products remains a grand challenge. Herein, we present a non-classical Fischer-Tropsch to olefins process featuring high carbon efficiency that realizes 80.1% olefins selectivity with ultralow total selectivity of CH4 and CO2 (<5%) at CO conversion of 45.8%. This is enabled by sodium-promoted metallic ruthenium (Ru) nanoparticles with negligible water-gas-shift reactivity. Change in the local electronic structure and the decreased reactivity of chemisorbed H species on Ru surfaces tailor the reaction pathway to favor olefins production. No obvious deactivation is observed within 550 hours and the pellet catalyst also exhibits excellent catalytic performance in a pilot-scale reactor, suggesting promising practical applications.