Direct Alcohol Fuel Cells: A Comparative Review of Acidic and Alkaline Systems

Berretti, Enrico; Osmieri, Luigi; Baglio, Vincenzo; Miller, Hamish A.; Filippi, Jonathan; Vizza, Francesco; Santamaria, Monica; Specchia, Stefania; Santoro, Carlo; Lavacchi, Alessandro

doi:10.1007/s41918-023-00189-3

Cited by 23 publications

(7 citation statements)

References 445 publications

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“…During OCV holding, acetone reduction could occur on Pt surfaces, poisoned with acetone, by forming a mixed potential with HOR, resulting in clean Pt surfaces. While the formation of a mixed potential in the cathode resulting from reactant crossover to the cathode has been reported to lower cell durability, ,, the hydrogen-driven mixed potential in the anode enhances the DIFC durability. We successfully validated our strategy conceptually to clean the poisoned surface via additives in the anode, which can be effective in bridging the gap between half-cell and full-cell.…”

Section: Resultsmentioning

confidence: 99%

Mixed Potential Driven Self-Cleaning Strategy in Direct Isopropanol Fuel Cells

Kim,

Son

et al. 2024

ACS Catal.

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A direct liquid organic hydrogen carrier fuel cell, such as the direct isopropanol fuel cell (DIFC), employs hydrogen to generate electricity through a combined process of dehydrogenation and hydrogen utilization. However, the performance decay of DIFC over time is a critical limitation. While the origin of deactivation and the strategy to overcome it have been investigated, the lack of understanding of the deactivation mechanism remains a significant bottleneck. In this study, cyclic voltammograms conducted in the half-cell (three-electrode system) exhibit a notable variation trend of degradation in isopropyl alcohol (IPA) oxidation depending on the potential window. This variation suggests surface cleaning processes based on acetone removal involving acetone oxidation and reduction, respectively. Based on this trend, a self-cleaning strategy via mixed potential between H 2 oxidation and acetone reduction is designed to remove poisoned acetone in the DIFC full-cell (two-electrode system). The enhanced durability observed in the modified DIFC, fueled by H 2 -saturated IPA, validates the self-cleaning process of the electrocatalyst in the anode, suggesting the feasibility of applying the mixed potential concept to enhance durability in full-cell systems.

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Section: Resultsmentioning

confidence: 99%

Mixed Potential Driven Self-Cleaning Strategy in Direct Isopropanol Fuel Cells

Kim,

Son

et al. 2024

ACS Catal.

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“…MOR is the key reaction in DMFCs, but the Pt/C catalyst suffers from poisoning by the *CO intermediate. − The effective way to reduce the poisoning of *CO for supported Pt catalysts is to appropriately downshift the d -band center of Pt, which can be achieved by alloying with transition metals (strain and ligand effects) or replacing the supports with electron-donating properties (electronic metal-support interaction). , Interestingly, the developed L1 2 -Pt 3 Ti-TiC catalyst can satisfy both of the above requirements. The electrocatalytic performance of the studied catalysts for MOR was evaluated in Ar-saturated 0.1 M HClO 4 solution containing 1.0 M CH 3 OH after being activated and cleaned in 0.1 M HClO 4 until stable cyclic voltammetry (CV) (Figures S22–S23).…”

Section: Resultsmentioning

confidence: 99%

Constructing Gradient Orbital Coupling to Induce Reactive Metal–Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation

Li,

Wang,

et al. 2024

J. Am. Chem. Soc.

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Reactive metal−support interaction (RMSI) is an emerging way to regulate the catalytic performance for supported metal catalysts. However, the induction of RMSI by the thermal reduction is often accompanied by the encapsulation effect on metals, which limits the mechanism research and applications of RMSI. In this work, a gradient orbital coupling construction strategy was successfully developed to induce RMSI in Pt-carbide system without a reductant, leading to the formation of L1 2 -Pt x M-MC y (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) intermetallic electrocatalysts. Density functional theory (DFT) calculations suggest that the gradient coupling of the d(M)-2p(C)-5d(Pt) orbital would induce the electron transfer from M to C covalent bonds to Pt NPs, which facilitates the formation of C vacancy (C v ) and the subsequent M migration (occurrence of RMSI). Moreover, the good correlation between the formation energy of C v and the onset temperature of RMSI in Pt-MC x systems proves the key role of nonmetallic atomic vacancy formation for inducing RMSI. The developed L1 2 -Pt 3 Ti-TiC catalyst exhibits excellent acidic methanol oxidation reaction activity, with mass activity of 2.36 A mg Pt −1 in half-cell and a peak power density of 187.9 mW mg Pt −1 in a direct methanol fuel cell, which is one of the best catalysts ever reported. DFT calculations reveal that L1 2 -Pt 3 Ti-TiC favorably weakens *CO absorption compared to Pt-TiC due to the change of the absorption site from Pt to Ti, which accounts for the enhanced MOR performance.

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“…Direct methanol fuel cells (DMFCs) have shown broad prospects as a new-generation power source due to their high energy density, environmental friendliness, and low operating temperature. − As the anodic reaction, the methanol oxidation reaction (MOR) is regarded as the bottleneck for DMFCs due to the sluggish reaction kinetics. − Accordingly, great attention has been focused on developing active and stable MOR catalysts. Up to date, the state-of-art MOR catalysts of platinum (Pt) group metals-based catalysts still suffer from various challenges, including the scarce reserve of Pt, insufficient catalytic activity and easily poisoned active sites, which greatly hinder the large-scale application of DMFCs. − For the Pt-based MOR catalysts, the adsorption energetics on CO* and OH* intermediates act as two essential reactivity descriptors for their catalytic activity, which determines the water dissociation rate and antipoisoning ability on active sites. − Therefore, designing the Pt sites with fine-tuned electronic configuration to achieve the desired adsorption energetics toward CO* and OH* intermediates is crucial but still challenging for realizing the industrialization of DMFCs.…”

Section: Introductionmentioning

confidence: 99%

Optimizing Intermediate Adsorption on Pt Sites via Triple-Phase Interface Electronic Exchange for Methanol Oxidation

Chen,

Wang,

Chen

et al. 2024

Inorg. Chem.

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For the most commonly applied platinum-based catalysts of direct methanol fuel cells, the adsorption ability toward reaction intermediates, including CO and OH, plays a vital role in their catalytic activity and antipoisoning in anodic methanol oxidation reaction (MOR). Herein, guided by a theoretical mechanism study, a favorable modulation of the electronic structure and intermediate adsorption energetics for Pt active sites is achieved by constructing the triple-phase interfacial structure between tin oxide (SnO 2 ), platinum (Pt), and nitrogen-doped graphene (NG). From the strong electronic exchange at the triple-phase interface, the adsorption ability toward MOR reaction intermediates on Pt sites could be efficiently optimized, which not only inhibits the adsorption of CO* on active sites but also facilitates the adsorption of OH* to strip the poisoning species from the catalyst surface. Accordingly, the resulting catalyst delivers excellent catalytic activity and antipoisoning ability for MOR catalysis. The mass activity reaches 1098 mA mg −1 Pt , 3.23 times of commercial Pt/C. Meanwhile, the initial potentials and main peak for CO oxidation are also located at a much lower potential (0.51 and 0.74 V) against commercial Pt/C (0.83 and 0.89 V).

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Direct Alcohol Fuel Cells: A Comparative Review of Acidic and Alkaline Systems

Cited by 23 publications

References 445 publications

Mixed Potential Driven Self-Cleaning Strategy in Direct Isopropanol Fuel Cells

Mixed Potential Driven Self-Cleaning Strategy in Direct Isopropanol Fuel Cells

Constructing Gradient Orbital Coupling to Induce Reactive Metal–Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation

Optimizing Intermediate Adsorption on Pt Sites via Triple-Phase Interface Electronic Exchange for Methanol Oxidation

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