Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution

Rhone P. Brocha Silalahi; Hao Liang; Yongsung Jo; Jian Hong Liao; Tzu Hao Chiu; Ying Yann Wu; Xiaoping Wang; Samia Kahlal; Qi Wang; Woojun Choi; Dongil Lee; Jean Yves Saillard; C. W. Liu

doi:10.1002/chem.202303755

Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution

Rhone P. Brocha Silalahi, Hao Liang, Yongsung Jo, Jian Hong Liao, Tzu Hao Chiu, Ying Yann Wu, Xiaoping Wang, Samia Kahlal, Qi Wang, Woojun Choi, Dongil Lee, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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

6 Scopus citations

Abstract

A structurally precise hydride-containing Pt-doped Cu-rich nanocluster [PtH₂Cu₁₄{S₂P(OⁱPr)₂}₆(CCPh)₆] (1) has been synthesized. It consists of a bicapped icosahedral Cu₁₄ cage that encapsulates a linear PtH₂ unit. Upon the addition of two equivalents of CF₃COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu₁₁{S₂P(OⁱPr)₂}₆(CCPh)₄] (2), which is a vertex-missing Cu₁₁ cuboctahedron encaging a PtH moiety, and [PtH₂Cu₁₁{S₂P(OⁱPr)₂}₆(CCPh)₃] (3), a distorted 3,3,4,4,4-pentacapped trigonal prismatic Cu₁₁ cage enclosing a PtH₂ unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm⁻²), a Tafel slope of 39 mV dec⁻¹, and consistent HER activity throughout 3000 cycles in 0.5 M H₂SO₄. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity.

Original language	English
Article number	e202303755
Journal	Chemistry - A European Journal
Volume	30
Issue number	13
DOIs	https://doi.org/10.1002/chem.202303755
State	Published - Mar 1 2024

Funding

This work was supported by the National Science and Technology Council of Taiwan (112‐2123‐M‐259‐001), the GENCI computing resource (grant A0090807367), the National Research Foundation of Korea grants (NRF‐2022R1A2C3003610 and Carbon‐to‐X Project No. 2020M3H7A1096388), and Single‐crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under contract no. DE‐AC05‐00OR22725 with UT‐Battelle, LLC. HL thanks the China Scholarship Council for a PhD grant.

Funders	Funder number
Office of Science
Oak Ridge National Laboratory
National Science and Technology Council	112‐2123‐M‐259‐001
National Research Foundation of Korea	2020M3H7A1096388, NRF‐2022R1A2C3003610
China Scholarship Council
Grand Équipement National De Calcul Intensif	A0090807367

Keywords

Copper
hydride
hydrogen evolution reaction
platinum

UN SDGs

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

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10.1002/chem.202303755

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Brocha Silalahi, R. P., Liang, H., Jo, Y., Liao, J. H., Chiu, T. H., Wu, Y. Y., Wang, X., Kahlal, S., Wang, Q., Choi, W., Lee, D., Saillard, J. Y., & Liu, C. W. (2024). Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution. Chemistry - A European Journal, 30(13), Article e202303755. https://doi.org/10.1002/chem.202303755

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title = "Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution",

abstract = "A structurally precise hydride-containing Pt-doped Cu-rich nanocluster [PtH2Cu14{S2P(OiPr)2}6(CCPh)6] (1) has been synthesized. It consists of a bicapped icosahedral Cu14 cage that encapsulates a linear PtH2 unit. Upon the addition of two equivalents of CF3COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu11{S2P(OiPr)2}6(CCPh)4] (2), which is a vertex-missing Cu11 cuboctahedron encaging a PtH moiety, and [PtH2Cu11{S2P(OiPr)2}6(CCPh)3] (3), a distorted 3,3,4,4,4-pentacapped trigonal prismatic Cu11 cage enclosing a PtH2 unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm−2), a Tafel slope of 39 mV dec−1, and consistent HER activity throughout 3000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity.",

keywords = "Copper, hydride, hydrogen evolution reaction, platinum",

author = "{Brocha Silalahi}, {Rhone P.} and Hao Liang and Yongsung Jo and Liao, {Jian Hong} and Chiu, {Tzu Hao} and Wu, {Ying Yann} and Xiaoping Wang and Samia Kahlal and Qi Wang and Woojun Choi and Dongil Lee and Saillard, {Jean Yves} and Liu, {C. W.}",

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year = "2024",

month = mar,

day = "1",

doi = "10.1002/chem.202303755",

language = "English",

volume = "30",

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T1 - Hydride-Containing Pt-doped Cu-rich Nanoclusters

T2 - Synthesis, Structure, and Electrocatalytic Hydrogen Evolution

AU - Brocha Silalahi, Rhone P.

AU - Liang, Hao

AU - Jo, Yongsung

AU - Liao, Jian Hong

AU - Chiu, Tzu Hao

AU - Wu, Ying Yann

AU - Wang, Xiaoping

AU - Kahlal, Samia

AU - Wang, Qi

AU - Choi, Woojun

AU - Lee, Dongil

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2024/3/1

Y1 - 2024/3/1

N2 - A structurally precise hydride-containing Pt-doped Cu-rich nanocluster [PtH2Cu14{S2P(OiPr)2}6(CCPh)6] (1) has been synthesized. It consists of a bicapped icosahedral Cu14 cage that encapsulates a linear PtH2 unit. Upon the addition of two equivalents of CF3COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu11{S2P(OiPr)2}6(CCPh)4] (2), which is a vertex-missing Cu11 cuboctahedron encaging a PtH moiety, and [PtH2Cu11{S2P(OiPr)2}6(CCPh)3] (3), a distorted 3,3,4,4,4-pentacapped trigonal prismatic Cu11 cage enclosing a PtH2 unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm−2), a Tafel slope of 39 mV dec−1, and consistent HER activity throughout 3000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity.

AB - A structurally precise hydride-containing Pt-doped Cu-rich nanocluster [PtH2Cu14{S2P(OiPr)2}6(CCPh)6] (1) has been synthesized. It consists of a bicapped icosahedral Cu14 cage that encapsulates a linear PtH2 unit. Upon the addition of two equivalents of CF3COOH to 1, two hydrido clusters are isolated. These clusters are [PtHCu11{S2P(OiPr)2}6(CCPh)4] (2), which is a vertex-missing Cu11 cuboctahedron encaging a PtH moiety, and [PtH2Cu11{S2P(OiPr)2}6(CCPh)3] (3), a distorted 3,3,4,4,4-pentacapped trigonal prismatic Cu11 cage enclosing a PtH2 unit. The electronic structure of 2, analyzed by Density Functional Theory, is a 2e superatom. The electrocatalytic activities of 1–3 for hydrogen evolution reaction (HER) were compared. Notably, Cluster 2 exhibited an exceptionally excellent HER activity within metal nanoclusters, with an onset potential of −0.03 V (at 10 mA cm−2), a Tafel slope of 39 mV dec−1, and consistent HER activity throughout 3000 cycles in 0.5 M H2SO4. Our study suggests that the accessible central Pt site plays a crucial role in the remarkable HER activity and may provide valuable insights for establishing correlations between catalyst structure and HER activity.

KW - Copper

KW - hydride

KW - hydrogen evolution reaction

KW - platinum

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U2 - 10.1002/chem.202303755

DO - 10.1002/chem.202303755

M3 - Article

AN - SCOPUS:85182237579

SN - 0947-6539

VL - 30

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 13

M1 - e202303755

ER -

Hydride-Containing Pt-doped Cu-rich Nanoclusters: Synthesis, Structure, and Electrocatalytic Hydrogen Evolution

Abstract

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Keywords

UN SDGs

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