Chlorine evolution reaction (CER) is a critical anode reaction in chlor-alkali electrolysis. Although precious metal-based mixed metal oxides (MMOs) have been widely used as CER catalysts, they suffer from the concomitant generation of oxygen during the CER. Herein, we demonstrate that atomically dispersed Pt-N sites doped on a carbon nanotube (Pt/CNT) can catalyse the CER with excellent activity and selectivity. The Pt/CNT catalyst shows superior CER activity to a Pt nanoparticle-based catalyst and a commercial Ru/Ir-based MMO catalyst. Notably, Pt/CNT exhibits near 100% CER selectivity even in acidic media, with low Cl concentrations (0.1 M), as well as in neutral media, whereas the MMO catalyst shows substantially lower CER selectivity. In situ electrochemical X-ray absorption spectroscopy reveals the direct adsorption of Cl on Pt-N sites during the CER. Density functional theory calculations suggest the PtNC site as the most plausible active site structure for the CER.
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http://dx.doi.org/10.1038/s41467-019-14272-1 | DOI Listing |
J Am Chem Soc
December 2024
Key Laboratory of Mesoscopic Chemistry of MOE and Jiangsu Provincial Laboratory for Nanotechnology, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
Engineering microstructures of Pt and understanding the related catalytic mechanism are critical to optimizing the performance for hydrogen evolution reaction (HER). Herein, Pt dispersion and coordination are precisely regulated on hierarchical nitrogen-doped carbon nanocages (hNCNCs) by a thermal-driven Pt migration, from edge-hosted Pt-NCl single sites in the initial Pt/hNCNC-70 °C catalyst to Pt clusters/nanoparticles and back to in-plane Pt-NC single sites. Thereinto, Pt-NCl presents the optimal HER activity (6 mV@10 mA cm) while Pt-NC shows poor HER activity (321 mV@10 mA cm) due to their different Pt coordination.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
State Key Laboratory of Advanced Chemical Power Sources, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Tianjin Key Lab of Biosensing & Molecular Recognition, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, College of Chemistry, Nankai University, Tianjin 300071, China.
Dual-atom catalysts (DACs) have garnered significant interest due to their high atom utilization and synergistic catalysis. However, developing a precise synthetic method for DACs and comprehending the underlying catalytic mechanisms remain challenging. In this study, we employ a photoinduced anchoring strategy to precisely synthesize PtCo DAC on graphitic carbon nitride (CN).
View Article and Find Full Text PDFChemSusChem
October 2024
Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova, Italy.
COF engineering with a built-in, high concentration of defined N-doped sites overcomes the "black-box" drawback of conventional trial-and-error N-doping methods (used in polymeric carbon nitride and graphene), that hamper a directed evolution of functional carbon interfaces based on structure-reactivity guidelines. The cutting-edge challenge is to dissect the many complex and interdependent functions that originate from reticular N-doping, including modification of the material optoelectronics, band alignments, interfacial contacts and co-localization of active-sites, producing a multiple-set of effectors that can all play a role to regulate photocatalysis. Herein, an ON-OFF gated photocatalytic H evolution (PHE) is dictated by the Pt-N-carbon active sites and probed with a dual COF platform, based on stable β-ketoenamine connectivities made of triformylphloroglucinol (Tp) as the acceptor knots and 1,4-diaminonaphtalene (Naph) or 5,8-diaminoisoquinoline (IsoQ) as donors.
View Article and Find Full Text PDFACS Omega
October 2024
Department of Physics, Federal University of Pelotas, PO Box 354, 96010-900 Pelotas, RS, Brazil.
Platinum (Pt) subnanoclusters have become pivotal in nanocatalysis, yet their molecular adsorption mechanisms, particularly on supported versus unsupported systems, remain poorly understood. Our study employs detailed density functional theory (DFT) calculations with D3 corrections to investigate molecular adsorption on Pt subnanoclusters, focusing on CO, NO, N, and O species. Gas-phase and graphene-supported scenarios are systematically characterized to elucidate adsorption mechanisms and catalytic potential.
View Article and Find Full Text PDFNat Commun
September 2024
Tianjin Key Laboratory of Brain Science and Neural Engineering, Academy of Medical Engineering and Translational Medicine, Tianjin University, Tianjin, China.
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