4.8 Article

Ternary Palladium-Boron-Phosphorus Alloy Mesoporous Nanospheres for Highly Efficient Electrocatalysis

Journal

ACS NANO
Volume 13, Issue 10, Pages 12052-12061

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsnano.9b06339

Keywords

metal-metalloid-nonmetal; alloys; mesoporous chemistry; catalytic kinetics; electrocatalysis

Funding

  1. Jiangsu Specially Appointed Professor Plan, Natural Science Foundation of Jiangsu Province [BK20180723]
  2. Priority Academic Program Development of Jiangsu Higher Education Institutions, National and Local Joint Engineering Research Center of Biomedical Functional Materials
  3. World Premier International Research Center Initiative on Materials Nanoarchitectonics (WPI-MANA) from MEXT in Japan
  4. U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical, Biological and Geological Sciences [DE-FG02-86ER13622.A000]
  5. Queensland node of the Australian National Fabrication Facility

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Alloying palladium (Pd) catalysts with various metalloid and nonmetal elements can improve their catalytic performance in different chemical reactions. However, current nanosynthesis methods can only generate Pd alloys containing one metalloid or nonmetal, which limits the types of element combinations that may be used to improve Pd-based nanocatalysts. Herein, we report a simple soft-templating synthetic strategy to co-alloy Pd with the metalloid boron (B) and the nonmetal phosphorus (P) to generate ternary PdBP mesoporous nanospheres (MSs) with three-dimensional dendritic frameworks. We use a one-step aqueous synthesis method where dimethylamine borane and sodium hypophosphite serve as the B and P sources, respectively, as well as the co-reducing agents to drive the nucleation and growth of ternary PdBP alloy on a sacrificial dioctadecyldimethylammonium chloride template. The concentration of metalloid to nonmetal and the diameters of dendritic MSs can be tailored. The synthetic protocol is also extended to other multicomponent PdMBP alloy MSs to generate different types of dendritic mesoporous frameworks. Boron and phosphorus are known to accelerate the kinetics of the electrochemical oxygen reduction reaction (ORR) and alcohol oxidation reactions (AORs), because their alloys promote the decomposition of oxygen-containing intermediates on Pd surfaces. The dendritic mesoporous morphology of the ternary PdBP MSs also accelerates electron/mass transfer and exposes numerous active sites, enabling better performance in the ORR and AORs. Extending the surfactant-templating synthetic route to multiple types of elements will enable the generation of libraries of multicomponent metal-metalloid-nonmetal alloy nanostructures with functions that are suitable for various targeted applications.

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