28-: A New Polyoxometalate Structural Family with Catalytic Hydrogen Evolution Activity

Hongjin Lv; Yingnan Chi; Jan Van Leusen; Paul Kögerler; Zheyuan Chen; John Bacsa; Yurii V. Geletii; Weiwei Guo; Tianquan Lian; Craig L. Hill

doi:10.1002/chem.201503010

^28-: A New Polyoxometalate Structural Family with Catalytic Hydrogen Evolution Activity

Hongjin Lv, Yingnan Chi, Jan Van Leusen, Paul Kögerler, Zheyuan Chen, John Bacsa, Yurii V. Geletii, Weiwei Guo, Tianquan Lian, Craig L. Hill^*

^*Corresponding author for this work

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

52 Citations (Scopus)

Abstract

A new structural polyoxometalate motif, [{Ni₄(OH)₃AsO₄}₄(B-α-PW₉O₃₄)₄]^28-, which contains the highest nuclearity structurally characterized multi-nickel-containing polyanion to date, has been synthesized and characterized by single-crystal X-ray diffraction, temperature-dependent magnetism and several other techniques. The unique central {Ni₁₆(OH)₁₂O₄(AsO₄)₄} core shows dominant ferromagnetic exchange interactions, with maximum χ_mT of 69.21 cm³ K mol^-1 at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water-compatible, noble-metal-free catalyst for H₂ production upon visible light irradiation (photosensitizer=[Ir(ppy)₂(dtbbpy)][PF₆]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time-solved luminescence and by static emission quenching.

Original language	English
Pages (from-to)	17363-17370
Number of pages	8
Journal	Chemistry - A European Journal
Volume	21
Issue number	48
DOIs	https://doi.org/10.1002/chem.201503010
Publication status	Published - 23 Nov 2015
Externally published	Yes

Keywords

hydrogen production
nickel
photocatalysis
polyoxometalates
temperature-dependent magnetism

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10.1002/chem.201503010

Cite this

@article{13a52e86187b475499f5569567bb0dbb,

title = "28-: A New Polyoxometalate Structural Family with Catalytic Hydrogen Evolution Activity",

abstract = "A new structural polyoxometalate motif, [{Ni4(OH)3AsO4}4(B-α-PW9O34)4]28-, which contains the highest nuclearity structurally characterized multi-nickel-containing polyanion to date, has been synthesized and characterized by single-crystal X-ray diffraction, temperature-dependent magnetism and several other techniques. The unique central {Ni16(OH)12O4(AsO4)4} core shows dominant ferromagnetic exchange interactions, with maximum χmT of 69.21 cm3 K mol-1 at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water-compatible, noble-metal-free catalyst for H2 production upon visible light irradiation (photosensitizer=[Ir(ppy)2(dtbbpy)][PF6]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time-solved luminescence and by static emission quenching.",

keywords = "hydrogen production, nickel, photocatalysis, polyoxometalates, temperature-dependent magnetism",

author = "Hongjin Lv and Yingnan Chi and {Van Leusen}, Jan and Paul K{\"o}gerler and Zheyuan Chen and John Bacsa and Geletii, {Yurii V.} and Weiwei Guo and Tianquan Lian and Hill, {Craig L.}",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2015",

month = nov,

day = "23",

doi = "10.1002/chem.201503010",

language = "English",

volume = "21",

pages = "17363--17370",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "48",

}

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T2 - A New Polyoxometalate Structural Family with Catalytic Hydrogen Evolution Activity

AU - Lv, Hongjin

AU - Chi, Yingnan

AU - Van Leusen, Jan

AU - Kögerler, Paul

AU - Chen, Zheyuan

AU - Bacsa, John

AU - Geletii, Yurii V.

AU - Guo, Weiwei

AU - Lian, Tianquan

AU - Hill, Craig L.

PY - 2015/11/23

Y1 - 2015/11/23

N2 - A new structural polyoxometalate motif, [{Ni4(OH)3AsO4}4(B-α-PW9O34)4]28-, which contains the highest nuclearity structurally characterized multi-nickel-containing polyanion to date, has been synthesized and characterized by single-crystal X-ray diffraction, temperature-dependent magnetism and several other techniques. The unique central {Ni16(OH)12O4(AsO4)4} core shows dominant ferromagnetic exchange interactions, with maximum χmT of 69.21 cm3 K mol-1 at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water-compatible, noble-metal-free catalyst for H2 production upon visible light irradiation (photosensitizer=[Ir(ppy)2(dtbbpy)][PF6]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time-solved luminescence and by static emission quenching.

AB - A new structural polyoxometalate motif, [{Ni4(OH)3AsO4}4(B-α-PW9O34)4]28-, which contains the highest nuclearity structurally characterized multi-nickel-containing polyanion to date, has been synthesized and characterized by single-crystal X-ray diffraction, temperature-dependent magnetism and several other techniques. The unique central {Ni16(OH)12O4(AsO4)4} core shows dominant ferromagnetic exchange interactions, with maximum χmT of 69.21 cm3 K mol-1 at 3.4 K. Significantly, this structurally unprecedented complex is an efficient, water-compatible, noble-metal-free catalyst for H2 production upon visible light irradiation (photosensitizer=[Ir(ppy)2(dtbbpy)][PF6]; sacrificial electron donor=triethylamine or triethanolamine). The highest turnover number of approximately 580, corresponding to a best quantum yield of approximately 4.07 %, is achieved when using triethylamine as electron donor in the presence of water. The mechanism of this photodriven process has been probed by time-solved luminescence and by static emission quenching.

KW - hydrogen production

KW - nickel

KW - photocatalysis

KW - polyoxometalates

KW - temperature-dependent magnetism

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