Direct hydrogenation of CO2 to formic acid using Ru supported Co3O4 oxide as an efficient heterogeneous catalyst

Naikwadi, Dhanaji R.; Tayade, Rajesh J.; Biradar, Ankush V.

doi:10.1016/j.mcat.2022.112875

“…The transmission electron microscopy (TEM) image of Ru/Co 3 O 4 further confirmed the high dispersion of Ru with an average particle size of ∼1 nm (Figure c). High resolution TEM (HRTEM) images (Figure d) of Ru/Co 3 O 4 showed Ru 0 (002) with an interplanar spacing of 0.214 nm and RuO 2 (101) with an interplanar spacing of 0.254 nm, − suggesting the coexistence of Ru 0 and RuO 2 . The SAED images (Figure S2) also showed the crystal planes of Ru 0 (002), Ru 0 (102), RuO 2 (110), and RuO 2 (101). , …”

Section: Resultsmentioning

confidence: 99%

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co₃O₄ Catalyst

Liu,

Zhou,

Wang

et al. 2024

ACS Catal.

4

0

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α-Hydroxyl acid production from biomass has emerged as a promising approach for biomass valorization but remains a long-standing challenge due to limited productivity. Herein, we established an innovative strategy for the coproduction of glyceric and glycolic acids from pentose feedstocks. Ru/Co 3 O 4 catalyst, possessing tunable Ru n+ /Ru 0 ratio and abundant oxygen vacancy, was found to promote the total yield of glyceric acid and glycolic acid (up to 65.9 C-mol % with a ∼1:1 molar ratio based on the initial carbon in the feedstock, the highest value among the state-of-the-art advances) at a mild temperature (70 °C). The results of the isotopic tracing experiments confirmed that xylose underwent C2−C3 cleavage, yielding glyceraldehyde and glycolaldehyde intermediates, which could be oxidized to produce glyceric acid and glycolic acid, respectively. In combination with density functional theory (DFT) calculations, it was revealed that Ru n+ and Ru 0 with an appropriate Ru n+ /Ru 0 ratio, in addition to oxygen vacancies, made a pronounced cooperative contribution to achieve complicated cascade reactions. Ru n+ was proven to be more favorable for xylose adsorption via the interaction with the −C�O, thereby accelerating the ring-opening reaction and C2−C3 cleavage, while Ru 0 , together with oxygen vacancies, mainly contributed to the activation of O 2 to produce active oxygen species that facilitated the immediate oxidation of intermediates. The results of this work may provide useful insights into catalyst design and potential directions to maximize carbon utilization in biomass valorization.

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Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water

Mandal,

Kumar,

Panda

et al. 2023

Angewandte Chemie

0

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In recent times, heterogenization of homogeneous molecular catalysts onto various porous solid support structures has attracted significant research focus as a method for combining the advantages of both homogeneous as well as heterogeneous catalysis. The design of highly efficient, structurally robust and reusable heterogenized single‐site catalysts for CO2 hydrogenation reaction is a critical challenge that needs to be accomplished to implement a sustainable and practical CO2‐looped renewable energy cycle. This study demonstrated a heterogenized catalyst [Ir‐HCP‐(B/TPM)] containing a molecular Ir–abnormal N‐heterocyclic carbene (Ir‐aNHC) catalyst self‐supported by hierarchical porous hyper‐crosslinked polymer (HCP), in catalytic hydrogenation of CO2 to inorganic formate (HCO2−) salt which is a prospective candidate for direct formate fuel cells (DFFC). By employing this unique and first approach of utilizing a directly‐knitted HCP‐based organometallic single‐site catalyst for CO2‐to‐HCO2− in aqueous medium, extremely high activity of single‐run turnover number (TON) up to 50816 was achieved which is the highest so far considering all the heterogeneous catalysts for this reaction in water. Additionally, the catalyst featured excellent reusability furnishing a cumulative TON of 285400 in 10 cycles with just 1.6% loss in activity per cycle. Overall, the new catalyst displayed attributes that are important for developing tangible catalysts for practical applications.

show abstract

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water

Mandal,

Kumar,

Panda

et al. 2023

View full text Add to dashboard Cite

In recent times, heterogenization of homogeneous molecular catalysts onto various porous solid support structures has attracted significant research focus as a method for combining the advantages of both homogeneous as well as heterogeneous catalysis. The design of highly efficient, structurally robust and reusable heterogenized single‐site catalysts for CO2 hydrogenation reaction is a critical challenge that needs to be accomplished to implement a sustainable and practical CO2‐looped renewable energy cycle. This study demonstrated a heterogenized catalyst [Ir‐HCP‐(B/TPM)] containing a molecular Ir–abnormal N‐heterocyclic carbene (Ir‐aNHC) catalyst self‐supported by hierarchical porous hyper‐crosslinked polymer (HCP), in catalytic hydrogenation of CO2 to inorganic formate (HCO2−) salt which is a prospective candidate for direct formate fuel cells (DFFC). By employing this unique and first approach of utilizing a directly‐knitted HCP‐based organometallic single‐site catalyst for CO2‐to‐HCO2− in aqueous medium, extremely high activity of single‐run turnover number (TON) up to 50816 was achieved which is the highest so far considering all the heterogeneous catalysts for this reaction in water. Additionally, the catalyst featured excellent reusability furnishing a cumulative TON of 285400 in 10 cycles with just 1.6% loss in activity per cycle. Overall, the new catalyst displayed attributes that are important for developing tangible catalysts for practical applications.

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Direct hydrogenation of CO2 to formic acid using Ru supported Co3O4 oxide as an efficient heterogeneous catalyst

Cited by 11 publications

References 36 publications

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co₃O₄ Catalyst

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co₃O₄ Catalyst

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water

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Direct hydrogenation of CO2 to formic acid using Ru supported Co3O4 oxide as an efficient heterogeneous catalyst

Cited by 11 publications

References 36 publications

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co3O4 Catalyst

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co3O4 Catalyst

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO2 Hydrogenation in Water

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO2 Hydrogenation in Water

Contact Info

Product

Resources

About

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co₃O₄ Catalyst

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co₃O₄ Catalyst

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water

Directly Knitted Hierarchical Porous Organometallic Polymer‐Based Self‐Supported Single‐Site Catalyst for CO₂ Hydrogenation in Water