Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate

Yiyao Tian; Alexey L. Kaledin; Daniel L. Collins-Wildman; Victoria G. Snider; Djamaladdin G. Musaev; Craig L. Hill; Anatoly I. Frenkel

doi:10.1021/acsanm.1c00813

Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate

Yiyao Tian
, Alexey L. Kaledin
, Daniel L. Collins-Wildman
, Victoria G. Snider
, Djamaladdin G. Musaev
, Craig L. Hill
, Anatoly I. Frenkel

Materials Science and Engineering

Stony Brook University

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

The nanoscale one-dimensional polymeric polyniobate K12[Ti2O2][SiNb12O40]·22H2O (KSiNb) rapidly hydrolyzes the gaseous organophosphorus nerve agent simulant dimethyl chlorophosphate (DMCP). A multimodal approach combining X-ray, IR and Raman spectroscopies and computation reveals that this reaction, involving the initial nucleophilic attack of polyoxometalate (POM) oxygen at phosphorus, is greatly modulated by the polyniobate counterions: the most negative and nucleophilic oxygen atoms in KSiNb, the Ti-O-Ti and Ti-O-Nb oxygen atoms, preferentially bind the potassium counterions, compelling the less negative oxygen atoms to become the nucleophiles. This heretofore unnoted paradigm of the POM counterion location and function could well impact a myriad of POM reaction studies.

Original language	English
Pages (from-to)	5649-5654
Number of pages	6
Journal	ACS Applied Nano Materials
Volume	4
Issue number	6
DOIs	https://doi.org/10.1021/acsanm.1c00813
State	Published - Jun 25 2021

Keywords

DRIFTS
X-ray absorption spectroscopy
counterion impacts
density functional theory
nerve agent
normal-mode analysis
polyniobates

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10.1021/acsanm.1c00813

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title = "Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate",

abstract = "The nanoscale one-dimensional polymeric polyniobate K12[Ti2O2][SiNb12O40]·22H2O (KSiNb) rapidly hydrolyzes the gaseous organophosphorus nerve agent simulant dimethyl chlorophosphate (DMCP). A multimodal approach combining X-ray, IR and Raman spectroscopies and computation reveals that this reaction, involving the initial nucleophilic attack of polyoxometalate (POM) oxygen at phosphorus, is greatly modulated by the polyniobate counterions: the most negative and nucleophilic oxygen atoms in KSiNb, the Ti-O-Ti and Ti-O-Nb oxygen atoms, preferentially bind the potassium counterions, compelling the less negative oxygen atoms to become the nucleophiles. This heretofore unnoted paradigm of the POM counterion location and function could well impact a myriad of POM reaction studies.",

keywords = "DRIFTS, X-ray absorption spectroscopy, counterion impacts, density functional theory, nerve agent, normal-mode analysis, polyniobates",

author = "Yiyao Tian and Kaledin, \{Alexey L.\} and Collins-Wildman, \{Daniel L.\} and Snider, \{Victoria G.\} and Musaev, \{Djamaladdin G.\} and Hill, \{Craig L.\} and Frenkel, \{Anatoly I.\}",

note = "Publisher Copyright: {\textcopyright}",

year = "2021",

month = jun,

day = "25",

doi = "10.1021/acsanm.1c00813",

language = "English",

volume = "4",

pages = "5649--5654",

journal = "ACS Applied Nano Materials",

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T1 - Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate

AU - Tian, Yiyao

AU - Kaledin, Alexey L.

AU - Collins-Wildman, Daniel L.

AU - Snider, Victoria G.

AU - Musaev, Djamaladdin G.

AU - Hill, Craig L.

AU - Frenkel, Anatoly I.

N1 - Publisher Copyright: ©

PY - 2021/6/25

Y1 - 2021/6/25

N2 - The nanoscale one-dimensional polymeric polyniobate K12[Ti2O2][SiNb12O40]·22H2O (KSiNb) rapidly hydrolyzes the gaseous organophosphorus nerve agent simulant dimethyl chlorophosphate (DMCP). A multimodal approach combining X-ray, IR and Raman spectroscopies and computation reveals that this reaction, involving the initial nucleophilic attack of polyoxometalate (POM) oxygen at phosphorus, is greatly modulated by the polyniobate counterions: the most negative and nucleophilic oxygen atoms in KSiNb, the Ti-O-Ti and Ti-O-Nb oxygen atoms, preferentially bind the potassium counterions, compelling the less negative oxygen atoms to become the nucleophiles. This heretofore unnoted paradigm of the POM counterion location and function could well impact a myriad of POM reaction studies.

AB - The nanoscale one-dimensional polymeric polyniobate K12[Ti2O2][SiNb12O40]·22H2O (KSiNb) rapidly hydrolyzes the gaseous organophosphorus nerve agent simulant dimethyl chlorophosphate (DMCP). A multimodal approach combining X-ray, IR and Raman spectroscopies and computation reveals that this reaction, involving the initial nucleophilic attack of polyoxometalate (POM) oxygen at phosphorus, is greatly modulated by the polyniobate counterions: the most negative and nucleophilic oxygen atoms in KSiNb, the Ti-O-Ti and Ti-O-Nb oxygen atoms, preferentially bind the potassium counterions, compelling the less negative oxygen atoms to become the nucleophiles. This heretofore unnoted paradigm of the POM counterion location and function could well impact a myriad of POM reaction studies.

KW - DRIFTS

KW - X-ray absorption spectroscopy

KW - counterion impacts

KW - density functional theory

KW - nerve agent

KW - normal-mode analysis

KW - polyniobates

UR - https://www.scopus.com/pages/publications/85108560493

U2 - 10.1021/acsanm.1c00813

DO - 10.1021/acsanm.1c00813

M3 - Article

SN - 2574-0970

VL - 4

SP - 5649

EP - 5654

JO - ACS Applied Nano Materials

JF - ACS Applied Nano Materials

IS - 6

ER -

Polyniobate Nanothreads for Decomposition of the Nerve Agent Simulant Dimethyl Chlorophosphate

Abstract

Keywords

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