Effect of Alkali‐ and Alkaline‐Earth‐Metal Promoters on Silica‐Supported Co−Fe Alloy for Autocatalytic CO<sub>2</sub> Fixation

Song, Youngdong; Beyazay, Tuğçe; Tüysüz, Harun

doi:10.1002/anie.202316110

Cited by 4 publications

(3 citation statements)

References 70 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

“…Co-based catalysts are widely studied for CO 2 fixation owing to their activity toward Fischer–Tropsch processes. Given the vital role of Co in the Acetyl-CoA pathway, where it donates methyl groups, , a deep understanding of CO 2 fixation over Co catalysts implies significant importance. Metallic Co exhibits strong hydrogenation ability, predominantly yielding fully hydrogenated products, namely, CH 4 .…”

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

See 2 more Smart Citations

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

Song,

Tüysüz

2024

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

The study of the origin of life requires a multifaceted approach to understanding where and how life arose on Earth. One of the most compelling hypotheses is the chemosynthetic origin of life at hydrothermal vents, as this condition has been considered viable for early forms of life. The continuous production of H 2 and heat by serpentinization generates reductive conditions at hydrothermal vents, in which CO 2 can be used to build large biomolecules. Although this involves surface catalysis and an autocatalytic process, in which solid minerals act as catalysts in the conversion of CO 2 to metabolically important organic molecules, the systematic investigation of heterogeneous catalysis to comprehend prebiotic chemistry at hydrothermal vents has not been undertaken. In this Account, we discuss geochemical CO 2 fixation to metabolic intermediates by synthetic minerals at hydrothermal vents from the perspective of heterogeneous catalysis. Ni and Fe are the most abundant transition metals at hydrothermal vents and occur in the active site of the enzymes carbon monoxide dehydrogenases/ acetyl coenzyme A synthases (CODH/ACS). Synthetic free-standing NiFe alloy nanoparticles can convert CO 2 to acetyl coenzyme A pathway intermediates such as formate, acetate, and pyruvate. The same alloy can further convert pyruvate to citramalate, which is essential in the biological citramalate pathway. Thermal treatment of Ni 3 Fe nanoparticles under NH 3 , which can occur in hydrothermal vents, results in Ni 3 FeN/Ni 3 Fe heterostructures. This catalyst has been demonstrated to produce prebiotic formamide and acetamide from CO 2 and H 2 O using Ni 3 FeN/Ni 3 Fe as both substrate and catalyst. In the process of serpentinization, Co can be reduced in the vicinity of olivine, a Mg−Fe silicate mineral. This produces CoFe and CoFe 2 with serpentine in nature, representing SiO 2 -supported CoFe alloys. In mimicking these natural minerals, synthetic SiO 2 -supported CoFe alloys demonstrate the same liquid products as NiFe alloys, namely, formate, acetate, and pyruvate under mild hydrothermal vent conditions. In contrast to the NiFe system, hydrocarbons up to C 6 were detected in the gas phase, which is also present in hydrothermal vents. The addition of alkali and alkaline-earth metals to the catalysts results in enhanced formate concentration, playing a promotional role in CO 2 reduction. Finally, Co was loaded onto ordered mesoporous SiO 2 after modification with cations to simulate the minerals found in hydrothermal vents. These catalysts were then investigated under diminished H 2 O concentration, revealing the conversion of CO 2 to CO, CH 4 , methanol, and acetate. Notably, the selectivity to metabolically relevant methanol was enhanced in the presence of cations that could generate and stabilize the methoxy intermediate. Calculation using the machine learning approach revealed the possibility of predicting the selectivity of CO 2 fixation when modifying mesoporous SiO 2 supports with heterocations. Our research demonstrates that min...

show abstract

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

Section: Solid Catalyst Development Strategies For Co2 Fixationmentioning

confidence: 99%

See 1 more Smart Citation

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

Song,

Tüysüz

2024

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

show abstract

Electrocatalytic reduction of nitrogen oxide species to ammonia

Liu,

Bai,

Bergmann

et al. 2024

Chem

View full text Add to dashboard Cite

Establishing Active Cu⁺–O–Mg²⁺ Sites at the Cu₂O/CuO Interface for Efficient Electroreduction of CO₂ to C₂₊ Products

Ji,

Zang,

Liu

et al. 2024

ACS Materials Lett.

View full text Add to dashboard Cite

Cu-based materials are regarded as effective electrocatalysts for CO 2 RR; however, Cu + , the active site for C−C coupling, is unstable under reduction conditions. Herein, Mg 2+ is doped into the Cu 2 O/CuO interface and generates high-activity Cu + − O-Mg 2+ sites following electrochemical activation. The electron-withdrawing effect of Mg 2+ in the Cu + −O-Mg 2+ site stabilizes Cu + and optimizes the reaction pathway for CO 2 RR. At a partial current density of 567.21 ± 5.18 mA cm −2 , the Faraday efficiency (FE) for C 2+ products can reach 81.03 ± 0.74%. In situ Raman and in situ infrared spectroscopy reveal that the Cu + −O-Mg 2+ site significantly enhances the coverage and stability of *CO, which contributes to the ultrahigh selectivity of CO 2 toward C 2+ products. Density functional theory (DFT) studies indicate that *CO 2 is readily adsorbed on the Cu + −O-Mg 2+ site, facilitating the more effective generation of *CO, which subsequently promotes the electrochemical C−C coupling step and accelerates the production of C 2+ products.

show abstract

Effect of Alkali‐ and Alkaline‐Earth‐Metal Promoters on Silica‐Supported Co−Fe Alloy for Autocatalytic CO₂ Fixation

Cited by 4 publications

References 70 publications

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

Electrocatalytic reduction of nitrogen oxide species to ammonia

Establishing Active Cu⁺–O–Mg²⁺ Sites at the Cu₂O/CuO Interface for Efficient Electroreduction of CO₂ to C₂₊ Products

Contact Info

Product

Resources

About

Effect of Alkali‐ and Alkaline‐Earth‐Metal Promoters on Silica‐Supported Co−Fe Alloy for Autocatalytic CO2 Fixation

Cited by 4 publications

References 70 publications

CO2 Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

CO2 Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

Electrocatalytic reduction of nitrogen oxide species to ammonia

Establishing Active Cu+–O–Mg2+ Sites at the Cu2O/CuO Interface for Efficient Electroreduction of CO2 to C2+ Products

Contact Info

Product

Resources

About

Effect of Alkali‐ and Alkaline‐Earth‐Metal Promoters on Silica‐Supported Co−Fe Alloy for Autocatalytic CO₂ Fixation

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

CO₂ Fixation to Prebiotic Intermediates over Heterogeneous Catalysts

Establishing Active Cu⁺–O–Mg²⁺ Sites at the Cu₂O/CuO Interface for Efficient Electroreduction of CO₂ to C₂₊ Products