A Mononuclear Tungsten Photocatalyst for H2 Production

Aron J. Huckaba; Hunter Shirley; Robert W. Lamb; Steve Guertin; Shane Autry; Hammad Cheema; Kallol Talukdar; Tanya Jones; Jonah W. Jurss; Amala Dass; Nathan I. Hammer; Russell H. Schmehl; Charles Edwin Webster; Jared H. Delcamp

doi:10.1021/acscatal.7b04242

A Mononuclear Tungsten Photocatalyst for H₂ Production

Aron J. Huckaba, Hunter Shirley, Robert W. Lamb, Steve Guertin, Shane Autry, Hammad Cheema, Kallol Talukdar, Tanya Jones, Jonah W. Jurss, Amala Dass, Nathan I. Hammer, Russell H. Schmehl, Charles Edwin Webster, Jared H. Delcamp

Chemistry

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

21 Scopus citations

Abstract

We report herein a mononuclear, homogeneous photocatalyst for H₂ production with sunlight. The synthesis and characterization of a (pyridyl)-N-heterocyclic carbene tungsten tetracarbonyl complex W(pyNHC)(CO)₄ is described, and its application as a precatalyst for photocatalytic generation of H₂ is evaluated. Electrochemical and photophysical studies were used to characterize and evaluate the precatalyst and in situ generated catalyst [W(pyNHC)(CO)₃] for the visible-light-driven production of H₂ in the presence of triflic acid and decamethylferrocene without an additional photosensitizer. Under irradiation with a solar-simulated spectrum, a catalyst turnover number (TON) of >17 in 3 h of reaction time is observed for the production of H₂ with this system, which compares favorably to a prior reported (multinuclear) homogeneous photocatalyst using visible light (4 TON). Photonic energy was found to be necessary to access the active catalysts from the precatalyst and in the catalytic cycle. A mechanism is detailed on the basis of a combined photophysical and computational approach.

Original language	English
Pages (from-to)	4838-4847
Number of pages	10
Journal	ACS Catalysis
Volume	8
Issue number	6
DOIs	https://doi.org/10.1021/acscatal.7b04242
State	Published - Jun 1 2018

Bibliographical note

Funding Information:
A.J.H., H.S., R.L., S.G., S.A., H.C., K.T., J.J., N.I.H., R.H.S., C.E.W., and J.H.D. thank the NSF for funding (OIA-1539035). T.J. and A.D. thank NSF for funding (CHE-1255519). Computations were performed at the Mississippi State University High Performance Computing Collaboratory and the Mississippi Center for Supercomputing Research. This study was also partly supported by Mississippi State University Office of Research and Economic Development. SG thanks the Louisiana Board of Regents Graduate Fellowship Program for award 020-GF-14.

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

Catalysis
Chemistry (all)

Access to Document

10.1021/acscatal.7b04242

Cite this

@article{0479617c5123431eb80b62f1a4e5483f,

title = "A Mononuclear Tungsten Photocatalyst for H2 Production",

abstract = "We report herein a mononuclear, homogeneous photocatalyst for H2 production with sunlight. The synthesis and characterization of a (pyridyl)-N-heterocyclic carbene tungsten tetracarbonyl complex W(pyNHC)(CO)4 is described, and its application as a precatalyst for photocatalytic generation of H2 is evaluated. Electrochemical and photophysical studies were used to characterize and evaluate the precatalyst and in situ generated catalyst [W(pyNHC)(CO)3] for the visible-light-driven production of H2 in the presence of triflic acid and decamethylferrocene without an additional photosensitizer. Under irradiation with a solar-simulated spectrum, a catalyst turnover number (TON) of >17 in 3 h of reaction time is observed for the production of H2 with this system, which compares favorably to a prior reported (multinuclear) homogeneous photocatalyst using visible light (4 TON). Photonic energy was found to be necessary to access the active catalysts from the precatalyst and in the catalytic cycle. A mechanism is detailed on the basis of a combined photophysical and computational approach.",

author = "Huckaba, {Aron J.} and Hunter Shirley and Lamb, {Robert W.} and Steve Guertin and Shane Autry and Hammad Cheema and Kallol Talukdar and Tanya Jones and Jurss, {Jonah W.} and Amala Dass and Hammer, {Nathan I.} and Schmehl, {Russell H.} and Webster, {Charles Edwin} and Delcamp, {Jared H.}",

note = "Funding Information: A.J.H., H.S., R.L., S.G., S.A., H.C., K.T., J.J., N.I.H., R.H.S., C.E.W., and J.H.D. thank the NSF for funding (OIA-1539035). T.J. and A.D. thank NSF for funding (CHE-1255519). Computations were performed at the Mississippi State University High Performance Computing Collaboratory and the Mississippi Center for Supercomputing Research. This study was also partly supported by Mississippi State University Office of Research and Economic Development. SG thanks the Louisiana Board of Regents Graduate Fellowship Program for award 020-GF-14. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = jun,

day = "1",

doi = "10.1021/acscatal.7b04242",

language = "English",

volume = "8",

pages = "4838--4847",

number = "6",

}

TY - JOUR

T1 - A Mononuclear Tungsten Photocatalyst for H2 Production

AU - Huckaba, Aron J.

AU - Shirley, Hunter

AU - Lamb, Robert W.

AU - Guertin, Steve

AU - Autry, Shane

AU - Cheema, Hammad

AU - Talukdar, Kallol

AU - Jones, Tanya

AU - Jurss, Jonah W.

AU - Dass, Amala

AU - Hammer, Nathan I.

AU - Schmehl, Russell H.

AU - Webster, Charles Edwin

AU - Delcamp, Jared H.

N1 - Funding Information: A.J.H., H.S., R.L., S.G., S.A., H.C., K.T., J.J., N.I.H., R.H.S., C.E.W., and J.H.D. thank the NSF for funding (OIA-1539035). T.J. and A.D. thank NSF for funding (CHE-1255519). Computations were performed at the Mississippi State University High Performance Computing Collaboratory and the Mississippi Center for Supercomputing Research. This study was also partly supported by Mississippi State University Office of Research and Economic Development. SG thanks the Louisiana Board of Regents Graduate Fellowship Program for award 020-GF-14. Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/6/1

Y1 - 2018/6/1

N2 - We report herein a mononuclear, homogeneous photocatalyst for H2 production with sunlight. The synthesis and characterization of a (pyridyl)-N-heterocyclic carbene tungsten tetracarbonyl complex W(pyNHC)(CO)4 is described, and its application as a precatalyst for photocatalytic generation of H2 is evaluated. Electrochemical and photophysical studies were used to characterize and evaluate the precatalyst and in situ generated catalyst [W(pyNHC)(CO)3] for the visible-light-driven production of H2 in the presence of triflic acid and decamethylferrocene without an additional photosensitizer. Under irradiation with a solar-simulated spectrum, a catalyst turnover number (TON) of >17 in 3 h of reaction time is observed for the production of H2 with this system, which compares favorably to a prior reported (multinuclear) homogeneous photocatalyst using visible light (4 TON). Photonic energy was found to be necessary to access the active catalysts from the precatalyst and in the catalytic cycle. A mechanism is detailed on the basis of a combined photophysical and computational approach.

AB - We report herein a mononuclear, homogeneous photocatalyst for H2 production with sunlight. The synthesis and characterization of a (pyridyl)-N-heterocyclic carbene tungsten tetracarbonyl complex W(pyNHC)(CO)4 is described, and its application as a precatalyst for photocatalytic generation of H2 is evaluated. Electrochemical and photophysical studies were used to characterize and evaluate the precatalyst and in situ generated catalyst [W(pyNHC)(CO)3] for the visible-light-driven production of H2 in the presence of triflic acid and decamethylferrocene without an additional photosensitizer. Under irradiation with a solar-simulated spectrum, a catalyst turnover number (TON) of >17 in 3 h of reaction time is observed for the production of H2 with this system, which compares favorably to a prior reported (multinuclear) homogeneous photocatalyst using visible light (4 TON). Photonic energy was found to be necessary to access the active catalysts from the precatalyst and in the catalytic cycle. A mechanism is detailed on the basis of a combined photophysical and computational approach.

UR - http://www.scopus.com/inward/record.url?scp=85046479618&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85046479618&partnerID=8YFLogxK

U2 - 10.1021/acscatal.7b04242

DO - 10.1021/acscatal.7b04242

M3 - Article

AN - SCOPUS:85046479618

SN - 2155-5435

VL - 8

SP - 4838

EP - 4847

JO - ACS Catalysis

JF - ACS Catalysis

IS - 6

ER -