Bi-metallic [Cu/Co(6mna)2]n metal organic chalcogenolate frameworks as high-performance electro-catalysts for dye-sensitized solar cells: a ligand-assisted bottom-up synthesis

Chun Wei Lai; Yu Chien Lee; Yi Zhen Jiang; Chia Her Lin; Gautam Kumar; Michael H. Huang; Chun Ting Li

doi:10.1039/d3ta04970a

Bi-metallic [Cu/Co(6mna)₂]_n metal organic chalcogenolate frameworks as high-performance electro-catalysts for dye-sensitized solar cells: a ligand-assisted bottom-up synthesis

Chun Wei Lai
, Yu Chien Lee
, Yi Zhen Jiang
, Chia Her Lin
, Gautam Kumar
, Michael H. Huang
, Chun Ting Li^*

^*Corresponding author for this work

Department of Chemistry

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

7 Citations (Scopus)

Abstract

Mercaptonicotinate-based metal organic chalcogenolate frameworks (MOFs), including [Cu₂(6mna)(6mn)NH₄]_n-NO₃, [Co₂(6mna)₂]_n-NO₃, [Co₂(6mna)₂]_n-Cl, [Cu/Co(6mna)₂]_n-NO₃, and [Cu/Co(6mna)₂]_n-Cl (6mna = 6-mercaptonicotinic acid; 6mn = 6-mercaptonicotinate), were newly introduced as the electro-catalytic counter electrodes in dye-sensitized solar cells (DSSCs). By using a ligand-assisted bottom-up synthesis, these five types of MOF films were covalently bonded to a conducting substrate to deliver their intrinsic electro-catalytic ability without any additives. The DSSCs coupled with all the carbon cloth/MOF electrodes showed a superior solar-to-electricity conversion efficiency (9.4%-10.0%) to the cell with a traditional carbon cloth/Pt electrode (9.3%), demonstrating their outstanding electrochemical activities. Heterogeneous bi-metallic MOFs, [Cu/Co(6mna)₂]_n-NO₃ and [Cu/Co(6mna)₂]_n-Cl, outperformed their mono-metallic counterparts by increasing film roughness/porosity and decreasing the activation energy for I⁻/I₃⁻. Their remarkable electrochemical performance was attributed to the successful synergistic effect, where [Cu₂(6mna)(6mn)NH₄]_n-NO₃ provided facile charge transfer via its 2D (-Cu-S-)_n planes, while [Co₂(6mna)₂]_n supplied large surface area and multiple electro-catalytic active sites through its helical (-Co-S-)_n chains. With the use of different redox mediators (iodide, Co-phenanthroline, and Cu-neocuproine), the optimal carbon cloth/[Cu/Co(6mna)₂]_n-Cl electrode also showed better electro-catalytic ability and long-term stability than carbon cloth/Pt. Under room light illumination, higher cell efficiencies were obtained at 1.0 klux (19.5% for an office), 3.0 klux (23.3% for a shopping window), and 6.0 klux (26.4% for a lampshade), revealing the potential of mercaptonicotinate-based bi-metallic MOFs to be applied in various electrochemical devices.

Original language	English
Pages (from-to)	1595-1608
Number of pages	14
Journal	Journal of Materials Chemistry A
Volume	12
Issue number	3
DOIs	https://doi.org/10.1039/d3ta04970a
Publication status	Published - 2023 Dec 4

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

SDG 7 Affordable and Clean Energy

ASJC Scopus subject areas

General Chemistry
Renewable Energy, Sustainability and the Environment
General Materials Science

Access to Document

10.1039/d3ta04970a

Cite this

Bi-metallic [Cu/Co(6mna)₂]_n metal organic chalcogenolate frameworks as high-performance electro-catalysts for dye-sensitized solar cells: a ligand-assisted bottom-up synthesis. / Lai, Chun Wei; Lee, Yu Chien; Jiang, Yi Zhen et al.
In: Journal of Materials Chemistry A, Vol. 12, No. 3, 04.12.2023, p. 1595-1608.

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

@article{67e142fc0a644213b1c97eed57c79e44,

title = "Bi-metallic [Cu/Co(6mna)2]n metal organic chalcogenolate frameworks as high-performance electro-catalysts for dye-sensitized solar cells: a ligand-assisted bottom-up synthesis",

abstract = "Mercaptonicotinate-based metal organic chalcogenolate frameworks (MOFs), including [Cu2(6mna)(6mn)NH4]n-NO3, [Co2(6mna)2]n-NO3, [Co2(6mna)2]n-Cl, [Cu/Co(6mna)2]n-NO3, and [Cu/Co(6mna)2]n-Cl (6mna = 6-mercaptonicotinic acid; 6mn = 6-mercaptonicotinate), were newly introduced as the electro-catalytic counter electrodes in dye-sensitized solar cells (DSSCs). By using a ligand-assisted bottom-up synthesis, these five types of MOF films were covalently bonded to a conducting substrate to deliver their intrinsic electro-catalytic ability without any additives. The DSSCs coupled with all the carbon cloth/MOF electrodes showed a superior solar-to-electricity conversion efficiency (9.4\%-10.0\%) to the cell with a traditional carbon cloth/Pt electrode (9.3\%), demonstrating their outstanding electrochemical activities. Heterogeneous bi-metallic MOFs, [Cu/Co(6mna)2]n-NO3 and [Cu/Co(6mna)2]n-Cl, outperformed their mono-metallic counterparts by increasing film roughness/porosity and decreasing the activation energy for I−/I3−. Their remarkable electrochemical performance was attributed to the successful synergistic effect, where [Cu2(6mna)(6mn)NH4]n-NO3 provided facile charge transfer via its 2D (-Cu-S-)n planes, while [Co2(6mna)2]n supplied large surface area and multiple electro-catalytic active sites through its helical (-Co-S-)n chains. With the use of different redox mediators (iodide, Co-phenanthroline, and Cu-neocuproine), the optimal carbon cloth/[Cu/Co(6mna)2]n-Cl electrode also showed better electro-catalytic ability and long-term stability than carbon cloth/Pt. Under room light illumination, higher cell efficiencies were obtained at 1.0 klux (19.5\% for an office), 3.0 klux (23.3\% for a shopping window), and 6.0 klux (26.4\% for a lampshade), revealing the potential of mercaptonicotinate-based bi-metallic MOFs to be applied in various electrochemical devices.",

author = "Lai, \{Chun Wei\} and Lee, \{Yu Chien\} and Jiang, \{Yi Zhen\} and Lin, \{Chia Her\} and Gautam Kumar and Huang, \{Michael H.\} and Li, \{Chun Ting\}",

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month = dec,

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doi = "10.1039/d3ta04970a",

language = "English",

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TY - JOUR

T1 - Bi-metallic [Cu/Co(6mna)2]n metal organic chalcogenolate frameworks as high-performance electro-catalysts for dye-sensitized solar cells

T2 - a ligand-assisted bottom-up synthesis

AU - Lai, Chun Wei

AU - Lee, Yu Chien

AU - Jiang, Yi Zhen

AU - Lin, Chia Her

AU - Kumar, Gautam

AU - Huang, Michael H.

AU - Li, Chun Ting

PY - 2023/12/4

Y1 - 2023/12/4

N2 - Mercaptonicotinate-based metal organic chalcogenolate frameworks (MOFs), including [Cu2(6mna)(6mn)NH4]n-NO3, [Co2(6mna)2]n-NO3, [Co2(6mna)2]n-Cl, [Cu/Co(6mna)2]n-NO3, and [Cu/Co(6mna)2]n-Cl (6mna = 6-mercaptonicotinic acid; 6mn = 6-mercaptonicotinate), were newly introduced as the electro-catalytic counter electrodes in dye-sensitized solar cells (DSSCs). By using a ligand-assisted bottom-up synthesis, these five types of MOF films were covalently bonded to a conducting substrate to deliver their intrinsic electro-catalytic ability without any additives. The DSSCs coupled with all the carbon cloth/MOF electrodes showed a superior solar-to-electricity conversion efficiency (9.4%-10.0%) to the cell with a traditional carbon cloth/Pt electrode (9.3%), demonstrating their outstanding electrochemical activities. Heterogeneous bi-metallic MOFs, [Cu/Co(6mna)2]n-NO3 and [Cu/Co(6mna)2]n-Cl, outperformed their mono-metallic counterparts by increasing film roughness/porosity and decreasing the activation energy for I−/I3−. Their remarkable electrochemical performance was attributed to the successful synergistic effect, where [Cu2(6mna)(6mn)NH4]n-NO3 provided facile charge transfer via its 2D (-Cu-S-)n planes, while [Co2(6mna)2]n supplied large surface area and multiple electro-catalytic active sites through its helical (-Co-S-)n chains. With the use of different redox mediators (iodide, Co-phenanthroline, and Cu-neocuproine), the optimal carbon cloth/[Cu/Co(6mna)2]n-Cl electrode also showed better electro-catalytic ability and long-term stability than carbon cloth/Pt. Under room light illumination, higher cell efficiencies were obtained at 1.0 klux (19.5% for an office), 3.0 klux (23.3% for a shopping window), and 6.0 klux (26.4% for a lampshade), revealing the potential of mercaptonicotinate-based bi-metallic MOFs to be applied in various electrochemical devices.

AB - Mercaptonicotinate-based metal organic chalcogenolate frameworks (MOFs), including [Cu2(6mna)(6mn)NH4]n-NO3, [Co2(6mna)2]n-NO3, [Co2(6mna)2]n-Cl, [Cu/Co(6mna)2]n-NO3, and [Cu/Co(6mna)2]n-Cl (6mna = 6-mercaptonicotinic acid; 6mn = 6-mercaptonicotinate), were newly introduced as the electro-catalytic counter electrodes in dye-sensitized solar cells (DSSCs). By using a ligand-assisted bottom-up synthesis, these five types of MOF films were covalently bonded to a conducting substrate to deliver their intrinsic electro-catalytic ability without any additives. The DSSCs coupled with all the carbon cloth/MOF electrodes showed a superior solar-to-electricity conversion efficiency (9.4%-10.0%) to the cell with a traditional carbon cloth/Pt electrode (9.3%), demonstrating their outstanding electrochemical activities. Heterogeneous bi-metallic MOFs, [Cu/Co(6mna)2]n-NO3 and [Cu/Co(6mna)2]n-Cl, outperformed their mono-metallic counterparts by increasing film roughness/porosity and decreasing the activation energy for I−/I3−. Their remarkable electrochemical performance was attributed to the successful synergistic effect, where [Cu2(6mna)(6mn)NH4]n-NO3 provided facile charge transfer via its 2D (-Cu-S-)n planes, while [Co2(6mna)2]n supplied large surface area and multiple electro-catalytic active sites through its helical (-Co-S-)n chains. With the use of different redox mediators (iodide, Co-phenanthroline, and Cu-neocuproine), the optimal carbon cloth/[Cu/Co(6mna)2]n-Cl electrode also showed better electro-catalytic ability and long-term stability than carbon cloth/Pt. Under room light illumination, higher cell efficiencies were obtained at 1.0 klux (19.5% for an office), 3.0 klux (23.3% for a shopping window), and 6.0 klux (26.4% for a lampshade), revealing the potential of mercaptonicotinate-based bi-metallic MOFs to be applied in various electrochemical devices.

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