Doping and Interfacial Engineering of MoSe₂ Nanosheets by NH₃ Plasma Promoted Pt for Methanol Electrolysis

Abstract

The electrochemical methanol−hydrogen transformation as a significant technique for hydrogen generation is limited by a low Pt catalytic efficiency. Herein, the doping and interfacial support engineering of MoSe 2 nanosheets by NH 3 plasma confined in mesoporous hollow-carbon-spheressupported Pt nanoparticles (Pt/N-MoSe 2 @MHCS) were demonstrated as a novel platform for catalyzing methanol electrolysis. Experiments and density functional theory (DFT) calculations confirm that the band structure of the Pt species is downshifted to weaken the adsorption energy of CO ad /H ad , resulting in improved CO-poisoning resistance and accelerated electrocatalytic kinetics. As a result, Pt/ N-MoSe 2 @MHCS shows the highest current density of 99.2 mA cm −2 for methanol oxidation and a low overpotential of 26 mV@10 mA cm −2 for hydrogen evolution. The methanol-assisted water electrolyzer assembled by Pt/N-MoSe 2 @MHCS showed a low cell voltage of 1070 mV to reach 10 mA cm −2 . This work provides novel guidance for the design of reasonable noble-metal catalysts in methanol electrolysis for hydrogen production.

Interfacial Push–Pull Dynamics Enable Rapid Had Desorption for Enhanced Formate Electrooxidation

“…The escalating urgency to address challenges such as fossil fuel depletion and environmental pollution has propelled the search for low-carbon, eco-friendly, and sustainable energy alternatives. − In this context, fuel cells, particularly for their zero carbon emissions, minimal pollution, and high energy conversion efficiency, stand out as a leading solution for future energy conversion technologies. − The direct formate fuel cell (DFFC) operating in alkaline conditions has garnered significant interest due to its theoretical potential, low toxicity, and uncomplicated structure. , Pd-based catalysts have been recognized for their substantial activity in catalyzing formate in alkaline environments and are notably resistant to poisoning by carbonaceous materials, like CO ad /CH x . − However, a critical limitation arises from the generation of adsorbed hydrogen (H ad ) during formate oxidation on these catalysts. H ad , as a significant intermediate, hinders the adsorption of HCOO – , which leads to a rapid decrease in catalytic efficiency and below-par performance in DFFCs. , …”

Ni2P Aerogels with Pt Single-Atom Doping Tune Competitive Adsorption for Boosted Methanol Electrooxidation

“…Metal aerogels (MAs), consisting of an assembly of individual building blocks to three-dimensional (3D) and self-supported network structures, have drawn tremendous attention in electrocatalysis and sensing, because of facile synthetic methods, tunable composition, and the perfect inheritance of aerogels. − Large surface areas endow MAs with abundant active sites and high porosity with interconnected backbones that can accelerate electron/mass transport. − Recently, single-atom doping has offered an effective opportunity for diverse catalytic reactions featuring modulated electronic structures of active sites. − Pt-based nanomaterials are usually employed to catalyze alcohol and they have excellent adsorption on organic molecules, therefore, it is possible to tune the adsorption ability of active sites and boost the reaction process. , In this regard, designing Ni-based MAs with single-atom Pt-doped building blocks is highly desirable for boosting the MOR performance and clarifying the competitive adsorption behavior between OH – and CH 3 OH, which, however, remains a major challenge.…”