Chemical synthesis of unconventional topologically close-packed intermetallic nanocrystals (NCs) remains a considerable challenge due to the limitation of large volume asymmetry between the components. Here, a series of unconventional intermetallic Frank-Kasper C15 phase IrM (M = rare earth metals La, Ce, Gd, Tb, Tm) NCs is successfully prepared via a molten-salt assisted reduction method as efficient electrocatalysts for hydrogen evolution reaction (HER). Compared to the disordered counterpart (A1-IrCe), C15-IrCe features higher Ir-Ce coordination number that leads to an electron-rich environment for Ir sites.
View Article and Find Full Text PDFReactive 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-PtM-MC (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) intermetallic electrocatalysts.
View Article and Find Full Text PDFStructurally ordered L1-PtM (M = Fe, Co, Ni and so on) intermetallic nanocrystals, benefiting from the chemically ordered structure and higher stability, are one of the best electrocatalysts used for fuel cells. However, their practical development is greatly plagued by the challenge that the high-temperature (>600 °C) annealing treatment necessary for realizing the ordered structure usually leads to severe particle sintering, morphology change and low ordering degree, which makes it very difficult for the gram-scale preparation of desirable PtM intermetallic nanocrystals with high Pt content for practical fuel cell applications. Here we report a new concept involving the low-melting-point-metal (M' = Sn, Ga, In)-induced bond strength weakening strategy to reduce E and promote the ordering process of PtM (M = Ni, Co, Fe, Cu and Zn) alloy catalysts for a higher ordering degree.
View Article and Find Full Text PDFDeveloping efficient and anti-corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal-support interaction (RMSI) as ORR catalysts, using Ni-doped cubic ZrO (Ni/ZrO) supported L1-PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt.
View Article and Find Full Text PDFSurface polarization under harsh electrochemical environments usually puts catalysts in a thermodynamically unstable state, which strictly hampers the thermodynamic stability of Pt-based catalysts in high-performance fuel cells. Here, we report a strategy by introducing electron buffers (variable-valence metals, M = Ti, V, Cr, and Nb) into intermetallic Pt alloy nanoparticle catalysts to suppress the surface polarization of Pt shells using the structurally ordered L1-M-PtFe as a proof of concept. Operando X-ray absorption spectra analysis suggests that with the potential increase, electron buffers, especially Cr, could facilitate an electron flow to form a electron-enriched Pt shell and thus weaken the surface polarization and tensile Pt strain.
View Article and Find Full Text PDFHydrogen produced from neutral seawater electrolysis faces many challenges including high energy consumption, the corrosion/side reactions caused by Cl, and the blockage of active sites by Ca/Mg precipitates. Herein, we design a pH-asymmetric electrolyzer with a Na exchange membrane for direct seawater electrolysis, which can simultaneously prevent Cl corrosion and Ca/Mg precipitation and harvest the chemical potentials between the different electrolytes to reduce the required voltage. In-situ Raman spectroscopy and density functional theory calculations reveal that water dissociation can be promoted with a catalyst based on atomically dispersed Pt anchored to Ni-Fe-P nanowires with a reduced energy barrier (by 0.
View Article and Find Full Text PDFFe-N-C represents the most promising non-precious metal catalysts (NPMCs) for the oxygen reduction reaction (ORR) in fuel cells, but often suffers from poor stability in acid due to the dissolution of metal sites and the poor oxidation resistance of carbon substrates. In this work, silicon-doped iron-nitrogen-carbon (Si/Fe-N-C) catalysts were developed by in situ silicon doping and metal-polymer coordination. It was found that Si doping could not only promote the density of Fe-N /C active sites but also elevated the content of graphitic carbon through catalytic graphitization.
View Article and Find Full Text PDFThe development of highly efficient and durable water electrolysis catalysts plays an important role in the large-scale applications of hydrogen energy. In this work, protrusion-rich Cu@NiRu core@shell nanotubes are prepared by a facile wet chemistry method and used for catalyzing hydrogen evolution reaction (HER) in an alkaline environment. The protrusion-like RuNi alloy shells with accessible channels and abundant defects possess a large surface area and can optimize the surface electronic structure through the electron transfer from Ni to Ru.
View Article and Find Full Text PDFThe large-scale commercialization of proton-exchange-membrane fuel cells (PEMFCs) is extremely limited by their costly platinum-group metals (PGMs) catalysts, which are used for catalyzing the sluggish oxygen reduction reaction (ORR) kinetics at the cathode. Among the reported PGM-free catalysts so far, metal-nitrogen-carbon (M-N /C) catalysts hold a great potential to replace PGMs catalysts for the ORR due to their excellent initial activity and low cost. However, despite tremendous progress in this field in the past decade, their further applications are restricted by fast degradation under practical conditions.
View Article and Find Full Text PDFExploiting platinum-group-metal (PGM)-free electrocatalysts with remarkable activity and stability toward oxygen reduction reaction (ORR) is of significant importance to the large-scale commercialization of proton exchange membrane fuel cells (PEMFCs). Here, a high-performance and anti-Fenton reaction cobalt-nitrogen-carbon (Co-N-C) catalyst is reported via employing double crosslinking (DC) hydrogel strategy, which consists of the chemical crosslinking between acrylic acid (AA) and acrylamide (AM) copolymerization and metal coordinated crosslinking between Co and P(AA-AM) copolymer. The resultant DC hydrogel can benefit the Co dispersion via chelated Co-N/O bonds and relieve metal agglomeration during the subsequent pyrolysis, resulting in the atomically dispersed Co-Nx/C active sites.
View Article and Find Full Text PDFNi-rich ternary layered oxides represent the most promising cathodes for lithium ion batteries (LIBs) due to their relatively large specific capacities and high energy/power densities. Unfortunately, their inherent chemical instability and surface side reactions during the charge/discharge processes lead to rapid capacity fading and poor cycling life, which seriously restrict their practical applications. Herein, we report a simple dual-modification strategy for preparing LiNi0.
View Article and Find Full Text PDFThe aim of this study was to explore the contribution of microbial community to cellulose degradation during cellulosic wastes composting. Three raw materials with different cellulose content were employed, including rice straws (RS), leaves (L) and mushroom dregs (MD). The cellulose degraded by 92.
View Article and Find Full Text PDFThis study investigated oxytetracycline (OTC) effects on nitrogen (N) transformation and bacterial community diversity during chicken manure composting. The addition of OTC inhibited nitrifying bacteria, resulted in a decrease in the transformation of NH-N to NO-N during composting, and affected in the order T3 (32.76%) > T2 (28.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2019
The commercialization of proton exchange membrane fuel cells (PEMFCs) relies on highly active and stable electrocatalysts for oxygen reduction reaction (ORR) in acid media. The most successful catalysts for this reaction are nanostructured Pt-alloy with a Pt-skin. The synthesis of ultrasmall and ordered L1 -PtCo nanoparticle ORR catalysts further doped with a few percent of metals (W, Ga, Zn) is reported.
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