WVI-OH functionality on polyoxometalates for water reduction to molecular hydrogen

Sateesh Mulkapuri; Athira Ravi; Subhabrata Mukhopadhyay; Sathish Kumar Kurapati; Vinaya Siby; Samar K. Das

doi:10.1039/d2qi00421f

W^VI-OH functionality on polyoxometalates for water reduction to molecular hydrogen

Sateesh Mulkapuri, Athira Ravi, Subhabrata Mukhopadhyay, Sathish Kumar Kurapati, Vinaya Siby, Samar K. Das

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

7 Scopus citations

Abstract

Grafting a W^VI-(OH)₂ functionality on the surface of polyoxometalates (POMs) makes the concerned POM compounds, Na₆[{Co^II(H₂O)₃}₂{W^VI(OH)₂}₂{(Bi^IIIW^VI₉O₃₃)₂}]·8H₂O (1) and Na₄(Himi)₂[{Mn^II(H₂O)₃}₂{W^VI(OH)₂}₂{(Bi^IIIW^VI₉O₃₃)₂}]·28H₂O (2) prominent heterogeneous electrocatalysts for water reduction to molecular hydrogen. We have identified that the W^VI-(OH)₂ functionality acts as the active site for electrocatalytic hydrogen evolution reaction (HER). The chances of in situ generation and participation of secondary species (metal nanoparticles etc.) in the present electrocatalysis have been eliminated by performing controlled experiments. The electrocatalysts 1 and 2 are stable enough towards HER up to 1000 cycles of cyclic voltammetric measurement and 10 hours chronoamperometry. The relevant turnover frequencies of 1 and 2 are 0.593 s⁻¹ and 0.634 s⁻¹ respectively exhibiting high efficiency towards electrocatalytic HER. This work has potential to generalize that POMs having M-OH functionality attached on its cluster surface would function as catalysts for HER.

Original language	English
Pages (from-to)	3566-3577
Number of pages	12
Journal	Inorganic Chemistry Frontiers
Volume	9
Issue number	14
DOIs	https://doi.org/10.1039/d2qi00421f
State	Published - 27 May 2022
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1039/d2qi00421f

Cite this

@article{e39b0ec342814816923406f48d908699,

title = "WVI-OH functionality on polyoxometalates for water reduction to molecular hydrogen",

abstract = "Grafting a WVI-(OH)2 functionality on the surface of polyoxometalates (POMs) makes the concerned POM compounds, Na6[{CoII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·8H2O (1) and Na4(Himi)2[{MnII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·28H2O (2) prominent heterogeneous electrocatalysts for water reduction to molecular hydrogen. We have identified that the WVI-(OH)2 functionality acts as the active site for electrocatalytic hydrogen evolution reaction (HER). The chances of in situ generation and participation of secondary species (metal nanoparticles etc.) in the present electrocatalysis have been eliminated by performing controlled experiments. The electrocatalysts 1 and 2 are stable enough towards HER up to 1000 cycles of cyclic voltammetric measurement and 10 hours chronoamperometry. The relevant turnover frequencies of 1 and 2 are 0.593 s−1 and 0.634 s−1 respectively exhibiting high efficiency towards electrocatalytic HER. This work has potential to generalize that POMs having M-OH functionality attached on its cluster surface would function as catalysts for HER.",

author = "Sateesh Mulkapuri and Athira Ravi and Subhabrata Mukhopadhyay and Kurapati, {Sathish Kumar} and Vinaya Siby and Das, {Samar K.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = may,

day = "27",

doi = "10.1039/d2qi00421f",

language = "English",

volume = "9",

pages = "3566--3577",

journal = "Inorganic Chemistry Frontiers",

issn = "2052-1545",

publisher = "Royal Society of Chemistry",

number = "14",

}

TY - JOUR

T1 - WVI-OH functionality on polyoxometalates for water reduction to molecular hydrogen

AU - Mulkapuri, Sateesh

AU - Ravi, Athira

AU - Mukhopadhyay, Subhabrata

AU - Kurapati, Sathish Kumar

AU - Siby, Vinaya

AU - Das, Samar K.

PY - 2022/5/27

Y1 - 2022/5/27

N2 - Grafting a WVI-(OH)2 functionality on the surface of polyoxometalates (POMs) makes the concerned POM compounds, Na6[{CoII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·8H2O (1) and Na4(Himi)2[{MnII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·28H2O (2) prominent heterogeneous electrocatalysts for water reduction to molecular hydrogen. We have identified that the WVI-(OH)2 functionality acts as the active site for electrocatalytic hydrogen evolution reaction (HER). The chances of in situ generation and participation of secondary species (metal nanoparticles etc.) in the present electrocatalysis have been eliminated by performing controlled experiments. The electrocatalysts 1 and 2 are stable enough towards HER up to 1000 cycles of cyclic voltammetric measurement and 10 hours chronoamperometry. The relevant turnover frequencies of 1 and 2 are 0.593 s−1 and 0.634 s−1 respectively exhibiting high efficiency towards electrocatalytic HER. This work has potential to generalize that POMs having M-OH functionality attached on its cluster surface would function as catalysts for HER.

AB - Grafting a WVI-(OH)2 functionality on the surface of polyoxometalates (POMs) makes the concerned POM compounds, Na6[{CoII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·8H2O (1) and Na4(Himi)2[{MnII(H2O)3}2{WVI(OH)2}2{(BiIIIWVI9O33)2}]·28H2O (2) prominent heterogeneous electrocatalysts for water reduction to molecular hydrogen. We have identified that the WVI-(OH)2 functionality acts as the active site for electrocatalytic hydrogen evolution reaction (HER). The chances of in situ generation and participation of secondary species (metal nanoparticles etc.) in the present electrocatalysis have been eliminated by performing controlled experiments. The electrocatalysts 1 and 2 are stable enough towards HER up to 1000 cycles of cyclic voltammetric measurement and 10 hours chronoamperometry. The relevant turnover frequencies of 1 and 2 are 0.593 s−1 and 0.634 s−1 respectively exhibiting high efficiency towards electrocatalytic HER. This work has potential to generalize that POMs having M-OH functionality attached on its cluster surface would function as catalysts for HER.

UR - http://www.scopus.com/inward/record.url?scp=85132233461&partnerID=8YFLogxK

U2 - 10.1039/d2qi00421f

DO - 10.1039/d2qi00421f

M3 - Article

AN - SCOPUS:85132233461

SN - 2052-1545

VL - 9

SP - 3566

EP - 3577

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

IS - 14

ER -