The influence of carbon monoxide on the voltammetric behaviour of nickel in acid solutions

et al. 2023

Preprint

The cost-effective production of green hydrogen is one of the most important challenges for a sustainable energy transition. To decrease the cost in the production of hydrogen through electrolysis, there are several obstacles that must be overcome. For instance, more active and stable anodes made of abundant and cheap materials will contribute to lowering the capital and operational expenditure of the process. It is well-known that the oxidation of water requires high overpotentials, which is the main limitation for the performance of the device. In this context, substituting the oxidation of water (OER) at the anode of electrolyzers by the oxidation of biomass-derived substances contribute to the overall process by decreasing the power input of the devices and, in some cases, by producing value-added chemicals. Herein, we re-visited some of the most important fundamental aspects of the (electro-)oxidation of alcohols and polyols on metal-based catalysts, focusing on reaction descriptors. Then, we moved to the (electro-)oxidation of these molecules on metal oxides, re-visiting some of the literature about their application in heterogeneous catalysis and for OER, to get insights about the relation of the structure of the materials and their activity. Due to the lack of fundamental knowledge about the electro-oxidation of alcohols and polyols on metallic oxides and to the vast literature about the use of perovskite oxides for OER, we propose to start systematic studies using perovskite oxides for the electrooxidation of alcohols and polyols. Consequently, we presented results for LaCoO3, LaFeO3, LaMnO3, and LaNiO3, and propose a mechanism for the electro-oxidation of glycerol based on the formation and reactivity of MOH(O) species. We believe that fundamental and systematic studies in this topic would permit the establishment of reaction descriptors, speeding up the searching for suitable materials for this reaction and paving the way for a most cost-effective production of green hydrogen.

Section: Langmuir-hinshelwood Mechanismmentioning

confidence: 96%

Perovskite oxides as an opportunity to systematically study the Electrooxidation of alcohols and Polyols on materials based on abundant elements: Learning from the experience using pure metals and metallic oxides in (Electro-)catalysis

et al. 2023

Preprint

“…The results discussed before qualitatively explain why, during the CO2RR: i) Pt, Pd and Ni are strongly poisoned by CO, ii) Au and Ag produce mainly CO (the interaction is too weak with this intermediate), and iii) Cu shows an intermediate behavior. These results are also valuable in the context of electrooxidation of alcohols and polyols; however, Cu and Ni cannot be evaluated in these conditions as Cu dissolves in acid and alkaline media and Ni dissolves in acid media at typical potentials for the electrooxidation of CO. Studies with Au 68,69 , Ag 70 and Ni 67,71,72 demonstrated a strong dependence of their activity with the pH, showing higher activity in alkaline media. It is interesting to note that the activity/interaction of Ag and Au increases in alkaline media due to the presence of hydroxide and/or the formation of oxides at their surfaces 68,70 , which was not considered in the computational experiments described before.…”

Section: Langmuir-hinshelwood Mechanismmentioning

confidence: 96%

Perovskite oxides as an opportunity to systematically study the Electrooxidation of alcohols and Polyols on materials based on abundant elements: Learning from the experience using pure metals and metallic oxides in (Electro-)catalysis

et al. 2022

Preprint

The cost-effective production of green hydrogen is one of the most important challenges for a sustainable energy transition. To decrease the cost in the production of hydrogen through electrolysis, there are several obstacles that must be overcome. For instance, more active and stable anodes made of abundant and cheap materials will contribute to lowering the capital and operational expenditure of the process. It is well-known that the oxidation of water requires high overpotentials, which is the main limitation for the performance of the device. In this context, we believe that substituting the oxidation of water (OER) at the anode of electrolyzers by the oxidation of biomass-derived substances could contribute to the overall process by decreasing the power input of the devices and, in some cases, by producing value-added chemicals. Herein, we re-visited some of the most important fundamental aspects of the (electro-)oxidation of alcohols and polyols on metal-based catalysts, focusing on reaction descriptors. Then, we moved to the (electro-)oxidation of these molecules on metal oxides, re-visiting some of the literature about their application in heterogeneous catalysis and for OER, to get insights about the relation of the structure of the materials and their activity. Due to the lack of fundamental knowledge about the electro-oxidation of alcohols and polyols on metallic oxides and to the vast literature about the use of perovskite oxides for OER, we propose to start systematic studies using perovskite oxides for the electrooxidation of alcohols and polyols. We believe that fundamental studies in this topic would permit the establishment of reaction descriptors, speeding up the searching for suitable materials for this reaction and paving the way for a most cost-effective production of green hydrogen.

“…Studies with Au, − Ag, , and Ni ,, demonstrated a strong dependence of their activity with the pH, showing higher activity in alkaline media. It was claimed that the activity/interaction of Ag and Au increases in alkaline media due to the presence of hydroxide and/or the formation of oxides at their surfaces; ,, however, other authors suggested that it could be a consequence of the effectively more negative potentials applied in alkaline media .…”

Section: Electrooxidation Of Alcohols and Polyols On Metalsmentioning

confidence: 97%

Perovskite Oxides as an Opportunity to Systematically Study the Electrooxidation of Alcohols and Polyols on Materials Based on Abundant Elements: Learning from the Experience Using Pure Metals and Metallic Oxides in Electrocatalysis

ACS Appl. Energy Mater.

et al. 2023

The cost-effective production of green hydrogen is one of the most important challenges for a sustainable energy transition. To decrease the cost of the production of hydrogen through electrolysis, there are several obstacles that must be overcome. For instance, more active and stable anodes made of abundant and cheap materials will contribute to lowering capital and operational expenditure. It is well known that the oxidation of water requires high overpotentials, which is the main limitation of the performance of the device. In this context, substituting the oxidation of water [oxygen evolution reaction (OER)] at the anode of electrolyzers by the oxidation of biomass-derived substances contributes to the overall process by decreasing the power input of the devices and, in some cases, by producing value-added chemicals. Herein, we revisited some of the most important fundamental aspects of the electrooxidation of alcohols and polyols on metal-based catalysts, focusing on reaction descriptors. Then, we moved to the electrooxidation of these molecules on metal oxides, revisiting some of the literature about their application in heterogeneous catalysis and for OER, to get insights about the relation of the structure of the materials and their activity. Due to the lack of fundamental knowledge about the electrooxidation of alcohols and polyols on metallic oxides and to the vast literature about the use of perovskite oxides for OER, we propose to start systematic studies using perovskite oxides for the electrooxidation of alcohols and polyols. Consequently, we presented results for LaCoO3, LaFeO3, LaMnO3, and LaNiO3 and proposed a mechanism for the electrooxidation of glycerol based on the formation and reactivity of MOH(O) species. We believe that fundamental and systematic studies on this topic would permit the establishment of reaction descriptors, speeding up the search for suitable materials for this reaction and paving the way for more cost-effective production of green hydrogen.