Adsorbed Formate is the Last Common Intermediate in the Dual-Path Mechanism of the Electrooxidation of Formic Acid

Betts, Alexander; Briega-Martos, Valentín; Cuesta, Ángel; Herrero, Enrique

doi:10.1021/acscatal.0c00791

Cited by 50 publications

(53 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…If this monodentate form is favored, the reaction rate is very fast and this reaction path is going directly to CO2 formation, leading to high formic acid oxidation currents (Figure 1B-C) [17]. In fact, under these conditions, the rate is limited by the availability of adsorption sites because is independent of the formate concentration [12].…”

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

“…The first one, the O-H bond breaking is a trivial step because it is involved in the acid base equilibria of the molecule. In fact, formate has been identified as the active species in the reaction [9][10][11][12], and thus, the only relevant bond that has to be cleaved is the C-H bond. The knowledge gained in the last years about this reaction has increased significantly using the combination of experimental and theoretical results and has been able to establish the rate determining step in the reaction.…”

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

“…First, it is clear that the effective cleavage of the C-H bond requires the adsorption of the molecule in the right configuration, that in which the H atom can interact with the surface. However, the most stable adsorbed configuration of formate, the bidentate form ( figure 1A), has been shown to be inactive for the oxidation [11,12,15] because the H atom is far from the surface and thus, the kinetic barrier for the cleavage of the C-H bond is very high ( Figure 1A) [2,16]. The activation of the C-H bond, then requires that formate is adsorbed in a monodentate configuration ( Figure 1A) [11].…”

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

“…Following the same scheme as that used for the FAOR, the first step would be to determine whether there is a strong interaction of methanol with the surface, because this interaction is required for an effective catalysis. For formate, the detection of adsorption modes was possible using Fourier-transform infrared spectroscopy (FTIR) in the total attenuated reflection (ATR) mode [10,24,25] or voltammetry at high scan rates [12,26]. In this case, since methanol oxidation currents are significantly smaller, the voltammetric profiles obtained in solutions with low methanol concentration can be used for that.…”

Section: Methanol Oxidation Reaction (Mor)mentioning

confidence: 99%

“…The formation of CH4 explains why in the isotopically labelled ethanol experiments the amount of 13 CO2 is always higher than that of 12 CO2, during the first scan. Only when the C-C bond cleavage takes place above 0.5 V, the 12 CH3 fragment yields adsorbed12 CO. This step requires the presence of adsorbed OH on the surface, highlight the importance of adsorbed OH in the oxidation of the molecule.…”

mentioning

confidence: 99%

See 4 more Smart Citations

On the oxidation mechanism of C1-C2 organic molecules on platinum. A comparative analysis

Rizo

Arán‐Ais

Herrero

2021

Current Opinion in Electrochemistry

Self Cite

View full text Add to dashboard Cite

The rationale design of better electrocatalysts for the oxidation of C1-C2 organic molecules requires the detailed knowledge of their oxidation mechanism. Pt single crystals are powerful tools to study, in a simple way, the surface structure effect on the different reaction pathways. Here, the oxidation mechanism of these molecules is compared so that the knowledge gained with the simpler mechanism is transferred in the analysis of the more complex ones. The goal is to design strategies so that the platinum electrodes improve their performance in their oxidation by the appropriate modification with other elements by attacking the bottlenecks in the reaction mechanism.

show abstract

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

Section: The Formic Acid Oxidation Reaction (Faor)mentioning

confidence: 99%

Section: Methanol Oxidation Reaction (Mor)mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

On the oxidation mechanism of C1-C2 organic molecules on platinum. A comparative analysis

Rizo

Arán‐Ais

Herrero

2021

Current Opinion in Electrochemistry

Self Cite

View full text Add to dashboard Cite

show abstract

Formic Acid to Power towards Low‐Carbon Economy

Dutta

Chatterjee

Cheng

et al. 2022

Advanced Energy Materials

112

View full text Add to dashboard Cite

The corresponding global annual carbon dioxide (CO 2 ) emissions had also increased from 23.1 gigatonnes of CO 2 (Gt CO2 ) in 2000 to 33.2 Gt CO2 in 2018. The excessive reliance on fossil fuels has caused the atmospheric CO 2 concentration to increase from the pre-industrial 280 ppm in the 18th century to the annual average of more than 410 ppm nowadays, which is found to be positively correlated to climate change. [2] To alleviate the environmental issues and to find viable alternatives for depleting fossil fuel reserves, the development and largescale deployment of clean and sustainable energy systems is of utmost importance. The development of suitable energy carriers is necessary to enable energy storage and distribution and to overcome the deficiency due to the intermittency of renewable energy sources such as solar and wind power. The use of H 2 has a great potential to diversify energy sectors and to prepare for the future implementation of low-carbon electricity and renewable energy. H 2 fuel cell (FC) technology is considered mature and regarded as the only technology to realize mobility without change of habits. As stated in the 2019 report by International Energy Agency to G20, H 2 is expected "to play a key role in a clean, secure and affordable energy future." [3] However, due to the lack of viable technologies for safe, efficient, and economical storage and transportation of H 2 , the applications of hydrogen have significantly been limited. [4] The storage and utilization of low-carbon electricity and decarbonization of transportation are essential components for the future energy transition into a low-carbon economy. While hydrogen has been identified as a potential energy carrier, the lack of viable technologies for safe and efficient storage and transportation of H 2 greatly limits its applications and deployment at scale. Formic acid (FA) is considered one of the promising H 2 energy carriers because of its high volumetric H 2 storage capacity of 53 g H 2 /L, and relatively low toxicity and flammability for convenient and low-cost storage and transportation. FA can be employed to generate electricity either in direct FA fuel cells (FCs) or indirectly as an H 2 source for hydrogen FCs. FA can enable large-scale chemical H 2 storage to eliminate energy-intensive and expensive processes for H 2 liquefaction and compression and thus to achieve higher efficiency and broader utilization. This perspective summarizes recent advances in catalyst development for selective dehydrogenation of FA and high-pressure H 2 production. The advantages and limitations of FA-to-power options are highlighted. Existing life cycle assessment (LCA) and economic analysis studies are reviewed to discuss the feasibility and future potential of FA as a fuel.

show abstract

Recent Advances of Single‐Atom‐Alloy for Energy Electrocatalysis

Shen

Wang

Zhao

et al. 2022

Advanced Energy Materials

View full text Add to dashboard Cite

In another example, intermetallics featuring smaller Pt [ , 8] Pd, [9] and Ir [10] atomic ensembles displayed higher formic acid oxidation reaction (FAOR) activity compared with corresponding monometallic nanoparticles. Thus, alloying is a feasible strategy to promote electrocatalytic performances. However, the random bimetallic alloy catalysts exhibit multiple types of atomic configurations, making it difficult to distinguish the most active coordination environment. In addition, the atomic utilization of noble metals, which usually working as the active sites, needs to be further promoted for common alloy catalysts.To achieve a full utilization of metallic atoms, single-atom catalysts (SACs) were developed in recent years. [11] Moreover, the significantly changed adsorption properties render SACs highly active in several reactions in which the metallic catalysts are inactive. For example, Fe, [12] Co, [13] Zn, [14] etc. SACs displayed superior ORR activity, enabling SACs promising cathodic catalysts in fuel cells. In the anodic reactions, Rh-N-C [15] and Ir-N-C [16] SACs exhibit ultrahigh FAOR activity surpassing state-ofthe-art Pd catalyst, while Rh and Ir nanoparticles are almost inert. Although SACs offer a full expose of metal sites, tuning the intrinsic activity is highly dependent on the substrates which anchored the single atomic sites. For instance, N-doped C anchored Pt SAC [16] displayed inferior FAOR performance while Au nanoparticles supported single atomic Pt [17] delivered excellent catalytic selectivity and activity, which may be attributed to the varying electronic structures of Pt. In view of the full utilization of active atoms in SACs and synergetic effects in alloys, combining their merits represents one of the most promising strategies to further promote electrocatalytic performance and acquiring structure-activity relationship in specific coordination environments. Thus, single-atom-alloys (SAAs), featuring with atomically dispersed metallic dopant atoms on the surface of metal hosts, [18] have been a kind of promising catalysts in heterogeneous catalysis. Commonly, the dopant atoms are active for specific reactions while the host metals are less reactive.The dopant element in SAA exhibits a free-atom-like electronic structure compared with host metal elements. [19] As shown in Figure 1a, the host metal Au exhibited the broad d-project density of states (DOS), while the dopant elements Pt and Ni exhibited the narrow d-project DOS, similar to the free-atom-like electronic states. Up to now, Pt-group metals are mainly employed as the dopants in SAAs to promote the Single-atom-alloys (SAAs), as an emerging kind of materials, combine the advantages of alloy and single-atom catalysts. The full atomic utilization of active sites and well-defined bonding environments in SAAs lead to superior electrocatalytic performance and give a deep insight into the structural-activity relationship. In this review, the recent advances of SAAs in various electrochemical reactions are highlighted for further...

show abstract

Adsorbed Formate is the Last Common Intermediate in the Dual-Path Mechanism of the Electrooxidation of Formic Acid

Cited by 50 publications

References 49 publications

On the oxidation mechanism of C1-C2 organic molecules on platinum. A comparative analysis

On the oxidation mechanism of C1-C2 organic molecules on platinum. A comparative analysis

Formic Acid to Power towards Low‐Carbon Economy

Recent Advances of Single‐Atom‐Alloy for Energy Electrocatalysis

Contact Info

Product

Resources

About