Abstract
A representative metal-organic framework, NU-1000, was functionalized with MoSx. The previously determined crystal structure of the material, named MoSx-SIM, consists of monometallic Mo(IV) ions with two sulfhydryl ligands. The metal ions are anchored to the framework by displacing protons presented by the-OH/-OH 2 groups on the Zr6 node. As shown previously, the MOF-supported complexes are electrocatalytic for hydrogen evolution from acidified water. The earlier electrocatalysis results, together with the nearly ideal formal potential of the Mo(IV/II) couple (i.e., nearly coincident with that of the hydrogen couple), and the physical proximity of UV-absorbing MOF linkers to the complexes, suggested to us that the linkers might behave photosensitizers for catalyst reduction, and subsequently, for H2 evolution from water. To our surprise, MoSx-SIM, when UV-illuminated in an aqueous buffer at near-neutral pH, displays a biphasic photocatalytic response: an initially slow rate of reaction, i.e. 0.56 mmol g -1 h -1 , followed by an increase to 4 mmol g -1 h -1 . Ex-situ catalyst examination revealed that nanoparticulate MoSx suspended within the reaction mixture is the actual catalyst. Thus, photo-assisted restructuring and detachment of the catalyst or pre-catalyst from the MOF node appears to be necessary for the catalyst to reduce water at neutral pH.
| Original language | English |
|---|---|
| Pages (from-to) | H3154-H3158 |
| Journal | Journal of the Electrochemical Society |
| Volume | 166 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - Jan 1 2019 |
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ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Renewable Energy, Sustainability and the Environment
- Surfaces, Coatings and Films
- Electrochemistry
- Materials Chemistry
Cite this
Molybdenum sulfide within a metal-organic framework for photocatalytic hydrogen evolution from water. / Noh, Hyunho; Yang, Ying; Ahn, Sol; Peters, Aaron W.; Farha, Omar K.; Hupp, Joseph T.
In: Journal of the Electrochemical Society, Vol. 166, No. 5, 01.01.2019, p. H3154-H3158.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Molybdenum sulfide within a metal-organic framework for photocatalytic hydrogen evolution from water
AU - Noh, Hyunho
AU - Yang, Ying
AU - Ahn, Sol
AU - Peters, Aaron W.
AU - Farha, Omar K.
AU - Hupp, Joseph T
PY - 2019/1/1
Y1 - 2019/1/1
N2 - A representative metal-organic framework, NU-1000, was functionalized with MoSx. The previously determined crystal structure of the material, named MoSx-SIM, consists of monometallic Mo(IV) ions with two sulfhydryl ligands. The metal ions are anchored to the framework by displacing protons presented by the-OH/-OH 2 groups on the Zr6 node. As shown previously, the MOF-supported complexes are electrocatalytic for hydrogen evolution from acidified water. The earlier electrocatalysis results, together with the nearly ideal formal potential of the Mo(IV/II) couple (i.e., nearly coincident with that of the hydrogen couple), and the physical proximity of UV-absorbing MOF linkers to the complexes, suggested to us that the linkers might behave photosensitizers for catalyst reduction, and subsequently, for H2 evolution from water. To our surprise, MoSx-SIM, when UV-illuminated in an aqueous buffer at near-neutral pH, displays a biphasic photocatalytic response: an initially slow rate of reaction, i.e. 0.56 mmol g -1 h -1 , followed by an increase to 4 mmol g -1 h -1 . Ex-situ catalyst examination revealed that nanoparticulate MoSx suspended within the reaction mixture is the actual catalyst. Thus, photo-assisted restructuring and detachment of the catalyst or pre-catalyst from the MOF node appears to be necessary for the catalyst to reduce water at neutral pH.
AB - A representative metal-organic framework, NU-1000, was functionalized with MoSx. The previously determined crystal structure of the material, named MoSx-SIM, consists of monometallic Mo(IV) ions with two sulfhydryl ligands. The metal ions are anchored to the framework by displacing protons presented by the-OH/-OH 2 groups on the Zr6 node. As shown previously, the MOF-supported complexes are electrocatalytic for hydrogen evolution from acidified water. The earlier electrocatalysis results, together with the nearly ideal formal potential of the Mo(IV/II) couple (i.e., nearly coincident with that of the hydrogen couple), and the physical proximity of UV-absorbing MOF linkers to the complexes, suggested to us that the linkers might behave photosensitizers for catalyst reduction, and subsequently, for H2 evolution from water. To our surprise, MoSx-SIM, when UV-illuminated in an aqueous buffer at near-neutral pH, displays a biphasic photocatalytic response: an initially slow rate of reaction, i.e. 0.56 mmol g -1 h -1 , followed by an increase to 4 mmol g -1 h -1 . Ex-situ catalyst examination revealed that nanoparticulate MoSx suspended within the reaction mixture is the actual catalyst. Thus, photo-assisted restructuring and detachment of the catalyst or pre-catalyst from the MOF node appears to be necessary for the catalyst to reduce water at neutral pH.
UR - http://www.scopus.com/inward/record.url?scp=85063162956&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85063162956&partnerID=8YFLogxK
U2 - 10.1149/2.0261905jes
DO - 10.1149/2.0261905jes
M3 - Article
AN - SCOPUS:85063162956
VL - 166
SP - H3154-H3158
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
SN - 0013-4651
IS - 5
ER -