Toward Electrocatalytic Methanol Oxidation Reaction: Longstanding Debates and Emerging Catalysts

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(26)

Published: Jan. 27, 2023

The study of direct methanol fuel cells (DMFCs) has lasted around 70 years, since the first investigation in early 1950s. Though enormous effort been devoted this field, it is still far from commercialization. oxidation reaction (MOR), as a semi-reaction DMFCs, bottleneck that restricts overall performance DMFCs. To date, there intense debate on complex six-electron reaction, but barely any reviews have systematically discussed topic. end, controversies and progress regarding electrocatalytic mechanisms, evaluations well design science toward MOR electrocatalysts are summarized. This review also provides comprehensive introduction recent development emerging with focus innovation alloy, core-shell structure, heterostructure, single-atom catalysts. Finally, perspectives future outlook mechanisms provided.

Language: Английский

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High‐Entropy Intermetallic PtRhBiSnSb Nanoplates for Highly Efficient Alcohol Oxidation Electrocatalysis

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(43)

Published: Sept. 5, 2022

The control of multimetallic ensembles at the atomic-level is challenging, especially for high-entropy alloys (HEAs) possessing five or more elements. Herein, one-pot synthesis hexagonal-close-packed (hcp) PtRhBiSnSb intermetallic (HEI) nanoplates with intrinsically isolated Pt, Rh, Bi, Sn, and Sb atoms reported, to boost electrochemical oxidation liquid fuels. Taking advantage these combined metals, well-defined HEI exhibit a remarkable mass activity 19.529, 15.558, 7.535 A mg-1Pt+Rh toward electrooxidation methanol, ethanol, glycerol in alkaline electrolytes, respectively, representing state-of-the-art multifunctional electrocatalyst alcohol reactions. In particular, achieves record-high methanol reaction (MOR) an environment. Theoretical calculations demonstrate that introduction fifth metal Rh enhances electron-transfer efficiency nanoplates, which contributes improved capability. Meanwhile, robust electronic structures active sites are achieved due synergistic protections from sites. This work offers significant research advances developing HEA delicate over compositions properties.

Language: Английский

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Recent advances in rare-earth-based materials for electrocatalysis

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(5), P. 967 - 1008

Published: March 3, 2022

Language: Английский

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Short‐Range Diffusion Enables General Synthesis of Medium‐Entropy Alloy Aerogels

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(30)

Published: May 25, 2022

Medium-entropy alloy aerogels (MEAAs) with the advantages of both multimetallic alloys and are promising new materials in catalytic applications. However, limited by immiscible behavior different metals, achieving single-phase MEAAs is still a grand challenge. Herein, general strategy for preparing ultralight 3D porous lowest density 39.3 mg cm-3 among metal reported, through combining auto-combustion subsequent low-temperature reduction procedures. The homogenous mixing precursors at ionic level makes short-range diffusion atoms possible to drive formation MEAAs. As proof concept catalysis, as-synthesized Ni50 Co15 Fe30 Cu5 exhibit high mass activity 1.62 A mg-1 specific 132.24 mA cm-2 toward methanol oxidation reactions, much higher than those low-entropy counterparts. In situ Fourier transform infrared NMR spectroscopies reveal that can enable highly selective conversion formate. Most importantly, methanol-oxidation-assisted MEAAs-based water electrolyzer achieve low cell voltage 1.476 V 10 making value-added formate anode H2 cathode, 173 mV lower traditional alkaline electrolyzers.

Language: Английский

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1D-2D hybridization: Nanoarchitectonics for grain boundary-rich platinum nanowires coupled with MXene nanosheets as efficient methanol oxidation electrocatalysts

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 450, P. 137932 - 137932

Published: July 6, 2022

Language: Английский

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Mixed‐Dimensional Pt–Ni Alloy Polyhedral Nanochains as Bifunctional Electrocatalysts for Direct Methanol Fuel Cells

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(2)

Published: Oct. 25, 2022

Pt nanocatalysts play a critical role in direct methanol fuel cells (DMFCs) due to their appropriate adsorption/desorption energy, yet suffer from an unbalanced relationship between size-dependent activity and stability. Herein, mixed-dimensional Pt-Ni alloy polyhedral nanochains (Pt-Ni PNCs) with ordered assembly of nanopolyhedra-nanowire-nanopolyhedra architecture are fabricated as bifunctional electrocatalysts for DMFCs, effectively alleviating the size effect. The PNCs exhibit 7.23 times higher mass anodic oxidation reaction (MOR) than that commercial Pt/C. In situ Fourier transform infrared spectroscopy CO stripping measurements demonstrate prominent stability resist poisoning. For cathodic oxygen reduction (ORR), positive half-wave potential exceeding Pt/C is achieved by PNCs, it can be well maintained 10 000 cycles negligible decay. designed nanostructure alleviate agglomeration dissolution problems 0D small-sized nanocrystals enrich surface atom steps active facets 1D chain-like nanostructures. This work provides proposed strategy improve catalytic performance Pt-based constructing novel interfacial relationships mixed dimensions imbalance caused effects.

Language: Английский

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Intermetallic Nanocrystals for Fuel-Cells-Based Electrocatalysis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12507 - 12593

Published: Nov. 1, 2023

Electrocatalysis underpins the renewable electrochemical conversions for sustainability, which further replies on metallic nanocrystals as vital electrocatalysts. Intermetallic have been known to show distinct properties compared their disordered counterparts, and long explored functional improvements. Tremendous progresses made in past few years, with notable trend of more precise engineering down an atomic level investigation transferring into practical membrane electrode assembly (MEA), motivates this timely review. After addressing basic thermodynamic kinetic fundamentals, we discuss classic latest synthetic strategies that enable not only formation intermetallic phase but also rational control other catalysis-determinant structural parameters, such size morphology. We demonstrate emerging nanomaterials potentially advancement energy electrocatalysis. Then, state-of-the-art characterizations representative electrocatalysts emphasis oxygen reduction reaction evaluated a MEA setup. summarize review by laying out existing challenges offering perspective future research directions toward practicing conversions.

Language: Английский

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Multiple Twin Boundary‐Regulated Metastable Pd for Ethanol Oxidation Reaction

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(8)

Published: Jan. 5, 2022

Abstract Abundant surface structural defects can endow electrocatalysts with extraordinary physical and chemical characteristics. Herein, metastable Pd nanoparticles (NPs) abundant twin boundaries (TBs) atomic steps (ASs) anchored on a carbon substrate (TS‐Pd/C) are directly synthesized by solid‐state thermal shock (TS) strategy. Molecular dynamics simulation indicates that the transient super cooling procedure after TS synthesis boost formation of TBs. Benefitting from TBs ASs, these NPs serve as an advanced electrocatalyst for ethanol oxidation reaction (EOR) superior reactivity, stability, CO tolerance in alkaline solutions, which far exceeds commercial Pd/C. The first‐principles calculations suggest defect structure dominated achieve spatial separation optimal adsorption sites OH. concentrate at to minimize number poisoned active sites. strong OH accelerate EOR process jointly promote improvement electrocatalytic reactivity.

Language: Английский

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Magnesium: properties and rich chemistry for new material synthesis and energy applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(6), P. 2145 - 2192

Published: Jan. 1, 2023

Magnesium (Mg) has many unique properties. The present review highlights the basic properties of Mg and its application in energy processes such as photocatalysis, electrocatalysis, storage, solar harvesting, hydrogen plasmonic, sensing.

Language: Английский

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Strong Electronic Interaction between Amorphous MnO₂ Nanosheets and Ultrafine Pd Nanoparticles toward Enhanced Oxygen Reduction and Ethylene Glycol Oxidation Reactions

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(21)

Published: Feb. 23, 2023

Abstract Strengthening the interface interaction between metal and support is an efficient strategy to improve intrinsic activity reduce amount of noble metal. Amorphization effective approach for enhancing metal‐support due numerous surface defects in amorphous structure. In this work, a Pd/a‐MnO 2 electrocatalyst containing ultrafine well‐dispersive Pd nanoparticles MnO nanosheets successfully synthesized via simple rapid wet chemical method. Differing from crystal counterpart (Pd/c‐MnO ), flexible structure can be more favorable electron transfer further enhance interaction. The synergism results downshift d‐band center, which beneficial desorption critical intermediates both oxygen reduction reaction (ORR) ethylene glycol oxidation (EGOR). Due lower * . OH energy surface, dissociation *OH facilitates formation H O ORR, thus demonstrating superior ORR performance comparable Pt/C. For EGOR, presence promotes adsorbed species, accelerates intermediate CO sites, exhibits excellent EGOR stability.

Language: Английский

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