Cobalt–copper based catalysts for higher terminal alcohols synthesis via Fischer–Tropsch reaction

Xiang, Yizhi; Kruse, Norbert

doi:10.1016/j.jechem.2016.09.014

Cited by 22 publications

(13 citation statements)

References 86 publications

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“…Interestingly, our group conducted DFT simulations and proved that CH could be formed on γ-AlOOH (001) surface via CHO + CO → CH + CO 2 , then CO was inserted into CH to form CHCO which finally underwent hydrogenation to produce ethanol. In addition, a Cu–ZnO–Al 2 O 3 catalyst was also prepared using Al 2 O 3 as the Al source in our previous work, the result showed that the selectivity of HA was only 7.2% . Furthermore, in this study, as shown in the above activity, the Cu component had a significant effect on CO conversion, while the Al component had more influence on the selectivity of HA.…”

Section: Discussionsupporting

confidence: 48%

“…In comparison, the catalysts with higher Cu proportion (e.g., Cu2.0 and Cu2.5) showed a slightly lower CO conversion and turnover frequency (TOF), but the catalyst stability greatly improved and no obvious deactivation occurred, the selectivity of HA even increased to 65 wt % for the Cu2.0 catalyst. It might be that there was an induction period for HA synthesis, which was also a basic law. , Meanwhile, as shown in Figure , the catalysts with various Al proportions exhibited relatively good stability, and the two catalysts (Al0.4, Al0.8) showed similar CO conversion and ethanol selectivity, whereas both the CO conversion and alcohol selectivity decreased for the Al1.0 catalyst. Among all the tested catalysts, the best performed catalyst was found to be the Cu2.0/Al0.8 catalyst, which exhibited better stability with time on stream as well as the highest HA selectivity of 65 wt %.…”

Section: Results and Discussionmentioning

confidence: 96%

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Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

Liu

Cui

Jia

et al. 2020

ACS Sustainable Chem. Eng.

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Currently, the Cu-based catalyst has become a promising candidate for ethanol and higher alcohols synthesis (HAs) from synthesis gas (H2 + CO), but all these catalysts contain F–T elements (e.g., Co and Fe) and alkalis because carbon chain growth reaction occurs on these metal components. Herein, two series of ternary CuZnAlOOH catalysts with various Cu and Al proportions were synthesized using a complete liquid-phase method and studied in the conversion of syngas in a slurry bed reactor. Significantly higher selectivity of ethanol (40 wt %) and HA (65 wt %) with approximately 20% CO conversion was achieved when the n (Cu)/n (Al) = 2/0.8, which was ascribed the highest copper surface area (S Cu) and the surface Cu content. It was found that the Cu component had a significant effect on CO conversion, while the Al component had more influence on the selectivity of HA. Besides, the coke deposition was discovered to be the main reason for catalyst deactivation. The generation of hydrocarbons and alcohols followed A–S–F distributions, which was consistent with a representative mechanism of HA generation by CO insertion into the CH x intermediate. A synergetic mechanism between Cu0–Cu+ and AlOOH active sites was proposed based on the characterization analysis and activity results, in which Cu0–Cu+ synergy acted as sites for H2 dissociative adsorption and associative adsorption of CO, while the AlOOH facilitated the dissociation of the C–O bond. Bifunctionality of the Cu and AlOOH active sites and their cooperation created their synergy in CO hydrogenation to ethanol and HA. This work provided us a new concept to understand and develop carbon chain growth mechanism, and it also could provide reference for other related carbon chain growth reactions.

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Section: Discussionsupporting

confidence: 48%

Section: Results and Discussionmentioning

confidence: 96%

Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

Liu

Cui

Jia

et al. 2020

ACS Sustainable Chem. Eng.

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“…Furthermore, it has been claimed that the closer the vicinity of both Cu–Co metal species, the better the synergistic effect will be . Fortunately, the Cu–Co bimetallic catalyst can be successfully achieved from several precursors mainly including crystalline porous materials (CPMs), − layered double hydroxides (LDHs), ,,,− oxalate co-precipitation oxides, − and perovskite morphology oxides. − As a new class of promising materials, CPMs have exhibited enhanced activity, selectivity, and stability owing to synergistic catalysis. In the case of LDHs, the Cu–Co NPs exhibited excellent catalytic performance for HAS because of uniformly distributed and highly dispersed Cu–Co particles at the nano-size level, as well as they were confined into the oxide structure derived from the LDH structure .…”

Section: Introductionmentioning

confidence: 99%

In Situ Encapsulated CuCo@M-SiO₂ for Higher Alcohol Synthesis from Biomass-Derived Syngas

Feng

Wang

Yan

et al. 2021

ACS Sustainable Chem. Eng.

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Higher alcohol synthesis (HAS) from biomass-derived syngas (CO/H2) is of considerable interest but has a challenge to achieve a satisfying yield, as it is a competitive reaction between C–C coupling and CO insertion. Herein, we employed a solvent (dihydric alcohol) coordination-assisted impregnation strategy to synthesize a series of catalysts with Cu and Co encapsulated in ordered mesoporous SiO2 (denoted as CuCo@M-SiO2). This synthesis strategy could effectively anchor Cu and Co cations at a close distance owing to the solvent coordination effect. Additionally, the carbon derived from the thermal decomposition (inert atmosphere) of the solvent ligand portrayed a critical role in in situ reduction of Cu and Co species and synchronous confinement. It also helped structural dispersant (“spacer”) and inhibited the aggregation of Cu nanoparticles (NPs). The as-prepared CuCo@M-SiO2 catalyst contained multiple types of synergistic active sites (Cu0, Co0, and Co n+) that collaborated with each other to enhance the higher alcohol yield. It is confirmed that the CO conversion and higher alcohol selectivity were closely related to solvent-assisted ligands. Among the selected solvent ligands (ethylene glycol, 1,2-propanediol, and 1,4-butanediol), the CuCo@M-SiO2 catalyst derived from 1,2-propanediol-assisted impregnation exhibited a remarkably catalytic performance because of the appropriate confinement effect with smaller CuCo NPs. Notably, the CO conversion was as high as 82.2% with space–time yield toward 16.1 mmol gcat –1 h–1 of ethanol. A narrow alcohol distribution of C1–C3-mixed alcohols was over 97.2%. These synthetic strategies may provide new avenues for designing effective and stable catalysts for HAS.

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“…[1] Distinct from traditional Cu/ZnO/Al 2 O 3 catalysts for CO 2 hydrogenation, [2] CoCu alloys show promising reactivity for the production of ethanol and other higher alcohols,possibly due to the bifunctionality introduced by the presence of cobalt and copper during hydrogenation reactions. [3] It is indicative that by changing the surface composition of CoCu alloys,t he reactivity and selectivity in hydrogenation reactions could be modified. An appropriate Co-Cu elemental distribution has been suggested crucial to produce higher alcohols with ah igh selectivity.…”

Section: Introductionmentioning

confidence: 99%

Moderate Surface Segregation Promotes Selective Ethanol Production in CO₂Hydrogenation Reaction over CoCu Catalysts

et al. 2021

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Cobalt-copper (CoCu) catalysts have industrial potential in CO/CO 2 hydrogenation reactions,and CoCu alloy has been elucidated as am ajor active phase during reactions. However,due to elemental surface segregation and dealloying phenomena, the actual surface morphology of CoCu alloy is still unclear.Combining theory and experiment, the dual effect of surface segregation and varied CO coverage over the CoCu(111) surface on the reactivity in CO 2 hydrogenation reactions is explored. The relationship between CÀOb ond scission and further hydrogenation of intermediate *CH 2 Owas discovered to be akey step to promote ethanol production. The theoretical investigation suggests that moderate Co segregation provides as uitable surface Co ensemble with lateral interactions of co-adsorbed *CO,l eading to promoted selectivity to ethanol, in agreement with theory-inspired experiments.

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Cobalt–copper based catalysts for higher terminal alcohols synthesis via Fischer–Tropsch reaction

Cited by 22 publications

References 86 publications

Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

In Situ Encapsulated CuCo@M-SiO₂ for Higher Alcohol Synthesis from Biomass-Derived Syngas

Moderate Surface Segregation Promotes Selective Ethanol Production in CO₂Hydrogenation Reaction over CoCu Catalysts

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Cobalt–copper based catalysts for higher terminal alcohols synthesis via Fischer–Tropsch reaction

Cited by 22 publications

References 86 publications

Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

Synergy between Active Sites of Ternary CuZnAlOOH Catalysts in CO Hydrogenation to Ethanol and Higher Alcohols

In Situ Encapsulated CuCo@M-SiO2 for Higher Alcohol Synthesis from Biomass-Derived Syngas

Moderate Surface Segregation Promotes Selective Ethanol Production in CO2Hydrogenation Reaction over CoCu Catalysts

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Product

Resources

About

In Situ Encapsulated CuCo@M-SiO₂ for Higher Alcohol Synthesis from Biomass-Derived Syngas

Moderate Surface Segregation Promotes Selective Ethanol Production in CO₂Hydrogenation Reaction over CoCu Catalysts