Efficient Screening of Bi–Metallic Electrocatalysts for Glycerol Valorization

Santos, Egon Campos dos; Araujo, Rafael B.; Valter, Mikael; Salazar-Alvarez, Germán; Johnsson, Mats; Bajdich, Michal; Abild‐Pedersen, Frank; Pettersson, Lars

doi:10.1016/j.electacta.2021.139283

Cited by 11 publications

(16 citation statements)

References 116 publications

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“…This concept is employed in a screening framework, which also accounts for thermal stability, bandgap, price, and toxicity as described in our earlier screening for bimetallic catalysts for glycerol oxidation. [ 23 ] In this context, we assumed that the correlation between GOR and the descriptors of spinel cobaltite could be applied to other oxides with similar local structure, that is, formed by TMs in octahedral or octahedral‐tetrahedral coordination. The Sabatier principle guide‐line for catalytic activity lies in the formation of chemical bonds between reaction intermediates and catalytic surfaces.…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Araujo

Qiu

et al. 2022

Advanced Energy Materials

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Electrochemical valorization of biomass waste (e.g., glycerol) for production of value‐added products (such as formic acid) in parallel with hydrogen production holds great potential for developing renewable and clean energy sources. Here, a synergistic effort between theoretical calculations at the atomic level and experiments to predict and validate a promising oxide catalyst for the glycerol oxidation reaction (GOR) are reported, providing a good example of designing novel, cost‐effective, and highly efficient electrocatalysts for producing value‐added products at the anode and high‐purity hydrogen at the cathode. The predicted CoMoO4 catalyst is experimentally validated as a suitable catalyst for GOR and found to perform best among the investigated metal (Mn, Co, Ni) molybdate counterparts. The potential required to reach 10 mA cm−2 is 1.105 V at 60 °C in an electrolyte of 1.0 m KOH with 0.1 m glycerol, which is 314 mV lower than for oxygen evolution. The GOR reaction pathway and mechanism based on this CoMoO4 catalyst are revealed by high‐performance liquid chromatography and in situ Raman analysis. The coupled quantitative analysis indicates that the CoMoO4 catalyst is highly active toward CC cleavage, thus presenting a high selectivity (92%) and Faradaic efficiency (90%) for formate production.

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Section: Resultsmentioning

confidence: 99%

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Araujo

Qiu

et al. 2022

Advanced Energy Materials

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“…At present, the major challenge to the generation of C 3 products is the lack of precise control over the selectivity of glycerol oxidation. To this end, developing electrocatalysts that are active, stable, and selective for electrovalorization into a carbon feedstock is an important research direction. , …”

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confidence: 99%

“…To this end, developing electrocatalysts that are active, stable, and selective for electrovalorization into a carbon feedstock is an important research direction. 19,20 To realize the transformation of excess glycerol into useful products, many chemical processes have been explored. Hightemperature processes can facilitate the reaction kinetics of glycerol, yet the product selectivity is poor.…”

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confidence: 99%

Direct 3D Printing of Binder-Free Bimetallic Nanomaterials as Integrated Electrodes for Glycerol Oxidation with High Selectivity for Valuable C₃ Products

Gao

Gillado

et al. 2022

ACS Nano

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Net-zero carbon strategies and green synthesis methodologies are key to realizing the United Nations’ sustainable development goals (SDGs) on a global scale. An electrocatalytic glycerol oxidation reaction (GOR) holds the promise of upcycling excess glycerol from biodiesel production directly into precious hydrocarbon commodities that are worth orders of magnitude more than the glycerol feedstock. Despite years of research on the GOR, the synthesis process of nanoscale electrocatalysts still involves (1) prohibitive heat input, (2) expensive vacuum chambers, and (3) emission of toxic liquid pollutants. In this paper, these knowledge gaps are closed via developing a laser-assisted nanomaterial preparation (LANP) process to fabricate bimetallic nanocatalysts (1) at room temperature, (2) under an ambient atmosphere, and (3) without liquid waste emission. Specifically, PdCu nanoparticles with adjustable Pd:Cu content supported on few-layer graphene can be prepared using this one-step LANP method with performance that can rival state-of-the-art GOR catalysts. Beyond exhibiting high GOR activity, the LANP-fabricated PdCu/C nanomaterials with an optimized Pd:Cu ratio further deliver an exclusive product selectivity of up to 99% for partially oxidized C3 products with value over 280000-folds that of glycerol. Through DFT calculations and in situ XAS experiments, the synergy between Pd and Cu is found to be responsible for the stability under GOR conditions and preference for C3 products of LANP PdCu. This dry LANP method is envisioned to afford sustainable production of multimetallic nanoparticles in a continuous fashion as efficient electrocatalysts for other redox reactions with intricate proton-coupled electron transfer steps that are central to the widespread deployment of renewable energy schemes and carbon-neutral technologies.

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“…The harmonic approximation was employed for the vibrational frequency calculations for all adsorbates and molecules. Following our previous publication, 36 Henry's law was used to link the gas phase pressure to the aqueous concentration using NIST-JANAF tables. Electrochemical environment was modelled based on the computational hydrogen electrode.…”

Section: Computational Detailsmentioning

confidence: 99%

“…24 Several studies have shown that noble metal catalysts such as Pd, Pt, Au, and Ag and their alloys are excellent for glycerol electrooxidation reaction (GEOR) with a great advantage of having lower electrode potential and high fraction percentage of C3 products (where the economic value of C3-chemicals is larger than C1chemicals). 25 In addition, the lower onset potential and higher stability over other noble metals make Pt an attractive catalyst. 21 Several experimental reports have emphasized the impact of high surface area of catalysts for better performance for water splitting and for methanol oxidation.…”

Section: Introductionmentioning

confidence: 99%

Effect of pore mesostructure on the electrooxidation of glycerol on Pt mesoporous catalysts

Anil

White

Santos

et al. 2023

Preprint

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Glycerol is a renewable chemical that has become widely available and inexpensive due to the increased production of biodiesel. Noble metal materials have shown to be effective catalysts for the production of hydrogen and value-added products through the electrooxidation of glycerol. In this work we develop three platinum systems with distinct pore mesostructures, e.g., hierarchical pores (HP), cubic pores (CP) and linear pores (LP); all with high electrochemically active surface area (ECSA). The ECSA-normalized GEOR catalytic activity of the systems follows HPC > LPC > CPC > commercial Pt/C. Regarding the oxidation products, we observe glyceric acid as the main three-carbon product (3C), with oxalic acids as the main two-carbon oxidation product. DFT-based theoretical calculations support the glyceraldehyde route going through tartronic acid towards oxalic acid and also help understanding why the dihydroxyacetone (DHA) route is active despite the absence of DHA amongst the observed oxidation products.

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Efficient Screening of Bi–Metallic Electrocatalysts for Glycerol Valorization

Cited by 11 publications

References 116 publications

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Direct 3D Printing of Binder-Free Bimetallic Nanomaterials as Integrated Electrodes for Glycerol Oxidation with High Selectivity for Valuable C₃ Products

Effect of pore mesostructure on the electrooxidation of glycerol on Pt mesoporous catalysts

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Efficient Screening of Bi–Metallic Electrocatalysts for Glycerol Valorization

Cited by 11 publications

References 116 publications

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO4—A Theoretically Predicted Catalyst

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO4—A Theoretically Predicted Catalyst

Direct 3D Printing of Binder-Free Bimetallic Nanomaterials as Integrated Electrodes for Glycerol Oxidation with High Selectivity for Valuable C3 Products

Effect of pore mesostructure on the electrooxidation of glycerol on Pt mesoporous catalysts

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Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Hydrogen Evolution Linked to Selective Oxidation of Glycerol over CoMoO₄—A Theoretically Predicted Catalyst

Direct 3D Printing of Binder-Free Bimetallic Nanomaterials as Integrated Electrodes for Glycerol Oxidation with High Selectivity for Valuable C₃ Products