POM‐Based Water Splitting Catalyst Under Acid Conditions Driven by Its Assembly on Carbon Nanotubes
Year: 2025
Type: article
Abstract: Development of efficient and stable bifunctional electrocatalysts for water electrolysis under acidic conditions is essential for sustainable hydrogen production. A novel vanadium polyoxometalate (POM)‐based material, Na 4 (H 2 O) 12 [(CH 2 OH) 3 CNH 3 ] 2 [V 10 O 28 ]·4H 2 O (1) is presented, incorporating non‐innocent cations and whose electrocatalytic activity can be switched from the production of oxygen to hydrogen through its assembly on carbon nanotubes (CNT). A physical mixture (1/CNT) shows remarkable oxygen evolution reaction (OER) activity, with an overpotential of 0.34 V at 10 mA cm − 2 , outperforming commercial IrO 2 (0.45 V) and approaching Ir/C (0.31 V), with 80% Faradaic efficiency. In contrast, directed assembly (1@CNT) unlocks TRIS ⁺= [(CH 2 OH) 3 CNH 3 ]⁺ groups functionality, enabling high hydrogen evolution reaction (HER) efficiency, with an onset potential of −0.07 V, close to Pt/C, and 94% Faradaic efficiency. Mechanistic studies, strongly supported by in‐operando confocal microscopy and theoretical calculations, reveal that the modulation of crystal interactions and the local microenvironment is key to orchestrating the OER/HER tuning. OER is proposed to proceed via an alcohol oxidation reaction (AOR), while HER benefits from TRIS⁺ moieties acting as a “proton sponge”. This work provides a compelling approach for rational design of bifunctional molecular electrocatalysts based on earth‐abundant elements and controlled nanoassembly, with clear relevance for advancing green hydrogen production technologies.
Source: Advanced Materials
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $6,070
Funders: European Commission, Ministerio de Ciencia e Innovación, Ministério da Ciência, Tecnologia e Ensino Superior, Consellería de Cultura, Educación e Ordenación Universitaria, Xunta de Galicia, Xunta de Galicia, Centro Singular de Investigación de Galicia, Centro de Investigação em Materiais Cerâmicos e Compósitos, European Research Council, Fundação para a Ciência e a Tecnologia, European Regional Development Fund
Awards: G1044294895, G1098384179, CICECO-Instituto de Materiais de Aveiro, G1248087530, G126583502, G1301230144, G141674513, G1496055848, G1593050779, G1792064735, G1814017720, G1857155500, G1918496035, G1939706375, G1939785963, G2233490251, G2316004153, G243576772, G2590264306, G2746783103, G3099176569, G3292045690, G3563331165, G3592153812, G3666820893, G3694284866, G3876637791, G3912226919, G404710190, G4180404498, G4333160874, G4448273050, G478805231, G4912376844, G5023816704, G5058569698, G5135910034, G5241663416, CICECO – Instituto de Materiais de Aveiro, G5353516086, CICECO-Instituto de Materiais de Aveiro, G6818627905, G6971996426, G804489863, G8050181529, G8108719017, G8207841777, G8373540578, G8461716579, G8588233800, G8730169892, G905768467
OpenAlex ID: W4416721609