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Download fileAzo(xy) vs Aniline Selectivity in Catalytic Nitroarene Reduction by Intermetallics: Experiments and Simulations
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posted on 2021-10-27, 18:45 authored by Carena
L. Daniels, Da-Jiang Liu, Marquix A. S. Adamson, Megan Knobeloch, Javier VelaIntermetallic
nanoparticles are promising catalysts in hydrogenation
and fuel cell technologies.
Much is known about the ability of intermetallic nanoparticles to
selectively reduce nitro vs alkene, alcohol, or halide
functional groups; less is known about their selectivity toward aniline vs azo or azoxy condensation products that result from the
reduction of a nitro group alone. Because azo(xy)arenes bear promise
as dyes, chemical stabilizers, and building blocks to functional materials
but can be difficult to isolate, developing high surface area nanoparticle
catalysts that display azo(xy) selectivity is desirable. To address
this question, we studied a family of nanocrystalline group 10 metal
(Pd, Pt)- and group 14 metal (Ge, Sn, Pb)-containing intermetallicsPd2Ge, Pd2Sn, Pd3Sn2, Pd3Pb, and PtSnin the catalytic reduction of nitroarenes.
In contrast to monometallic Au, Pt, and Pd nanoparticles and ″random″
PdxSn1 – x nanoalloys, which are selective for aniline, nanoparticles
of atomically precise intermetallic Pd2Ge, Pd2Sn, Pd3Sn2, and PtSn prefer an indirect condensation
pathway and have a high selectivity for the azo(xy) products. The
only exception is Pd3Pb, the most active among the intermetallic
nanoparticles studied here, which is instead selective for aniline.
Employing a novel application of molecular dynamicsbased on
machine learned potentials within a DeePMD frameworkto heterogeneous
catalysis, we are able to identify key reaction species on the different
types of catalysts employed, furthering our understanding of the unique
selectivity of these materials. By demonstrating how intermetallic
nanoparticles can be as active yet more selective than other more
traditional catalysts, this work provides new physical insights and
opens new opportunities in the use of these materials in other important
chemical transformations and applications.
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selectively reduce nitroopens new opportunitiesnitro group aloneindirect condensation pathwaygroup 14 metalfuel cell technologiesimportant chemical transformationshalide functional groupsdeepmd framework azoxy condensation productssimulations intermetallic nanoparticles3 sub2 subcatalytic nitroarene reductionselectivity toward anilineazo ( xyintermetallic nanoparticles studiedintermetallic nanoparticlesx vs ptsn chemical stabilizerscatalytic reductionsub ><> subunique selectivitytraditional catalystsptsn preferpromising catalystsnovel applicationmonometallic auhigh selectivityheterogeneous catalysisfunctional materialsdifferent typescatalysts employedbuilding blocksaniline selectivityactive yetactive among1 –