Interfacial engineering of 1D Pt/CeVO4@TiO2 heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction

Sayed Nauman Shah; Asad Mumtaz; Safdar Ali; Sani Zahra; Azhar Mahmood; Hina Sajid; Samrin Sayed; Qamir Ullah Niazi; Sabahat Sardar; Mujeeb Khan; Mohammad Rafe Hatshan; Syed Farooq Adil; Shahid Iqbal

doi:10.1016/j.molstruc.2025.142638

Interfacial engineering of 1D Pt/CeVO₄@TiO₂ heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction

Sayed Nauman Shah
, Asad Mumtaz
, Safdar Ali
, Sani Zahra
, Azhar Mahmood
, Hina Sajid
, Samrin Sayed
, Qamir Ullah Niazi
, Sabahat Sardar
, Mujeeb Khan
, Mohammad Rafe Hatshan
, Syed Farooq Adil
, Shahid Iqbal

CBI Green Chemicals and Energy Centre

Research output: Journal Publication › Article › peer-review

2 Citations (Scopus)

Abstract

1-D Pt/CeVO₄/TiO₂ heterostructures were designed to investigate the photoexcited charge separation and transportation by tailoring CeVO₄ over 1D TiO₂ nanorods to investigate methanol oxidation reaction (MOR) occurring on Pt nanoparticles. Structural, morphological, optical, electro-chemical and photo-electrochemical properties of the 1-D Pt/CeVO₄/TiO₂ heterojunctions are explored. Upon tuning CeVO₄ loading at the interface of 1D Pt-TiO₂ heterojunction, MOR is boosted by 50 % as observed from the highest photocurrent density of 12.49 mA/cm² under illumination in comparison to current density of 8.04 mA/cm² under dark for Pt/15-CeVO₄/TiO₂ sandwich-based heterojunction and 500 % in comparison to non-sandwich Pt/TiO₂ nanorods (1.98 mA/cm²) against Ag/AgCl. At 15 SILAR cycles of CeVO₄ modification, the ideal ratio of Pt dispersion to active site accessibility is reached as evidenced by the highest ECSA (15.38 m²/g Pt), the best mass activity (4.96 mA mg⁻¹ Pt), and the highest j^geo (8.04 mA cm⁻²) of Pt/15-CeVO₄/TiO₂. Furthermore, the diffusion coefficient of electron transfer is found to be 67.69×10⁻⁵ cm²s⁻¹ under dark which is enhanced to 104.67×10⁻⁵ cm²s⁻¹ for Pt/15-CeVO₄/TiO₂ under light. Noticeably, 15 SILAR layers of CeVO₄ over TiO₂ nanorods act as an efficient substrate of type-II heterojunction scheme to facilitate the methanol oxidation reaction activity of Pt potentially in Pt/15-CeVO₄/TiO₂ nanorods. Also, fluorescence spectra showed least electron/hole pair recombination with 15 SILAR layers of CeVO₄ over TiO₂ nanorods, evidencing the optimized penetration depth of electrons. Tuning CeVO₄@1D TiO₂ nanorods not only controlled solar spectrum sequestering but also contributed to decrease the Pt-CO bond strength via effective charge transfer in Pt/CeVO₄/TiO₂ by working as a cocatalyst. Such an interfacial engineering paved its way to explore other photocatalytic heterojunctions.

Original language	English
Article number	142638
Journal	Journal of Molecular Structure
Volume	1342
DOIs	https://doi.org/10.1016/j.molstruc.2025.142638
Publication status	Published - 15 Oct 2025

Free Keywords

5-Scheme heterojunctions
CO poisoning
Effective charge transfer
Interfacial engineering
Interfacial interactions
Noble metals
Pt/CeVO/@TiO heterojunction
S-scheme heterojunctions
Type-II heterojunction
Z-Scheme heterojunctions

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1016/j.molstruc.2025.142638

Cite this

Shah, S. N., Mumtaz, A., Ali, S., Zahra, S., Mahmood, A., Sajid, H., Sayed, S., Niazi, Q. U., Sardar, S., Khan, M., Hatshan, M. R., Adil, S. F., & Iqbal, S. (2025). Interfacial engineering of 1D Pt/CeVO₄@TiO₂ heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction. Journal of Molecular Structure, 1342, Article 142638. https://doi.org/10.1016/j.molstruc.2025.142638

@article{dea60a73149f4224b659fe5836af4c92,

title = "Interfacial engineering of 1D Pt/CeVO4@TiO2 heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction",

abstract = "1-D Pt/CeVO4/TiO2 heterostructures were designed to investigate the photoexcited charge separation and transportation by tailoring CeVO4 over 1D TiO2 nanorods to investigate methanol oxidation reaction (MOR) occurring on Pt nanoparticles. Structural, morphological, optical, electro-chemical and photo-electrochemical properties of the 1-D Pt/CeVO4/TiO2 heterojunctions are explored. Upon tuning CeVO4 loading at the interface of 1D Pt-TiO2 heterojunction, MOR is boosted by 50 \% as observed from the highest photocurrent density of 12.49 mA/cm2 under illumination in comparison to current density of 8.04 mA/cm2 under dark for Pt/15-CeVO4/TiO2 sandwich-based heterojunction and 500 \% in comparison to non-sandwich Pt/TiO2 nanorods (1.98 mA/cm2) against Ag/AgCl. At 15 SILAR cycles of CeVO₄ modification, the ideal ratio of Pt dispersion to active site accessibility is reached as evidenced by the highest ECSA (15.38 m²/g Pt), the best mass activity (4.96 mA mg⁻¹ Pt), and the highest jgeo (8.04 mA cm⁻²) of Pt/15-CeVO₄/TiO₂. Furthermore, the diffusion coefficient of electron transfer is found to be 67.69×10−5 cm2s−1 under dark which is enhanced to 104.67×10−5 cm2s−1 for Pt/15-CeVO4/TiO2 under light. Noticeably, 15 SILAR layers of CeVO4 over TiO2 nanorods act as an efficient substrate of type-II heterojunction scheme to facilitate the methanol oxidation reaction activity of Pt potentially in Pt/15-CeVO4/TiO2 nanorods. Also, fluorescence spectra showed least electron/hole pair recombination with 15 SILAR layers of CeVO4 over TiO2 nanorods, evidencing the optimized penetration depth of electrons. Tuning CeVO4@1D TiO2 nanorods not only controlled solar spectrum sequestering but also contributed to decrease the Pt-CO bond strength via effective charge transfer in Pt/CeVO4/TiO2 by working as a cocatalyst. Such an interfacial engineering paved its way to explore other photocatalytic heterojunctions.",

keywords = "5-Scheme heterojunctions, CO poisoning, Effective charge transfer, Interfacial engineering, Interfacial interactions, Noble metals, Pt/CeVO/@TiO heterojunction, S-scheme heterojunctions, Type-II heterojunction, Z-Scheme heterojunctions",

author = "Shah, \{Sayed Nauman\} and Asad Mumtaz and Safdar Ali and Sani Zahra and Azhar Mahmood and Hina Sajid and Samrin Sayed and Niazi, \{Qamir Ullah\} and Sabahat Sardar and Mujeeb Khan and Hatshan, \{Mohammad Rafe\} and Adil, \{Syed Farooq\} and Shahid Iqbal",

note = "Publisher Copyright: {\textcopyright} 2025",

year = "2025",

month = oct,

day = "15",

doi = "10.1016/j.molstruc.2025.142638",

language = "English",

volume = "1342",

journal = "Journal of Molecular Structure",

issn = "0022-2860",

publisher = "Elsevier B.V.",

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Shah, SN, Mumtaz, A, Ali, S, Zahra, S, Mahmood, A, Sajid, H, Sayed, S, Niazi, QU, Sardar, S, Khan, M, Hatshan, MR, Adil, SF & Iqbal, S 2025, 'Interfacial engineering of 1D Pt/CeVO₄@TiO₂ heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction', Journal of Molecular Structure, vol. 1342, 142638. https://doi.org/10.1016/j.molstruc.2025.142638

TY - JOUR

T1 - Interfacial engineering of 1D Pt/CeVO4@TiO2 heterojunction for superior electrocatalytic and photoelectrocatalytic activity of methanol oxidation reaction

AU - Shah, Sayed Nauman

AU - Mumtaz, Asad

AU - Ali, Safdar

AU - Zahra, Sani

AU - Mahmood, Azhar

AU - Sajid, Hina

AU - Sayed, Samrin

AU - Niazi, Qamir Ullah

AU - Sardar, Sabahat

AU - Khan, Mujeeb

AU - Hatshan, Mohammad Rafe

AU - Adil, Syed Farooq

AU - Iqbal, Shahid

PY - 2025/10/15

Y1 - 2025/10/15

N2 - 1-D Pt/CeVO4/TiO2 heterostructures were designed to investigate the photoexcited charge separation and transportation by tailoring CeVO4 over 1D TiO2 nanorods to investigate methanol oxidation reaction (MOR) occurring on Pt nanoparticles. Structural, morphological, optical, electro-chemical and photo-electrochemical properties of the 1-D Pt/CeVO4/TiO2 heterojunctions are explored. Upon tuning CeVO4 loading at the interface of 1D Pt-TiO2 heterojunction, MOR is boosted by 50 % as observed from the highest photocurrent density of 12.49 mA/cm2 under illumination in comparison to current density of 8.04 mA/cm2 under dark for Pt/15-CeVO4/TiO2 sandwich-based heterojunction and 500 % in comparison to non-sandwich Pt/TiO2 nanorods (1.98 mA/cm2) against Ag/AgCl. At 15 SILAR cycles of CeVO₄ modification, the ideal ratio of Pt dispersion to active site accessibility is reached as evidenced by the highest ECSA (15.38 m²/g Pt), the best mass activity (4.96 mA mg⁻¹ Pt), and the highest jgeo (8.04 mA cm⁻²) of Pt/15-CeVO₄/TiO₂. Furthermore, the diffusion coefficient of electron transfer is found to be 67.69×10−5 cm2s−1 under dark which is enhanced to 104.67×10−5 cm2s−1 for Pt/15-CeVO4/TiO2 under light. Noticeably, 15 SILAR layers of CeVO4 over TiO2 nanorods act as an efficient substrate of type-II heterojunction scheme to facilitate the methanol oxidation reaction activity of Pt potentially in Pt/15-CeVO4/TiO2 nanorods. Also, fluorescence spectra showed least electron/hole pair recombination with 15 SILAR layers of CeVO4 over TiO2 nanorods, evidencing the optimized penetration depth of electrons. Tuning CeVO4@1D TiO2 nanorods not only controlled solar spectrum sequestering but also contributed to decrease the Pt-CO bond strength via effective charge transfer in Pt/CeVO4/TiO2 by working as a cocatalyst. Such an interfacial engineering paved its way to explore other photocatalytic heterojunctions.

AB - 1-D Pt/CeVO4/TiO2 heterostructures were designed to investigate the photoexcited charge separation and transportation by tailoring CeVO4 over 1D TiO2 nanorods to investigate methanol oxidation reaction (MOR) occurring on Pt nanoparticles. Structural, morphological, optical, electro-chemical and photo-electrochemical properties of the 1-D Pt/CeVO4/TiO2 heterojunctions are explored. Upon tuning CeVO4 loading at the interface of 1D Pt-TiO2 heterojunction, MOR is boosted by 50 % as observed from the highest photocurrent density of 12.49 mA/cm2 under illumination in comparison to current density of 8.04 mA/cm2 under dark for Pt/15-CeVO4/TiO2 sandwich-based heterojunction and 500 % in comparison to non-sandwich Pt/TiO2 nanorods (1.98 mA/cm2) against Ag/AgCl. At 15 SILAR cycles of CeVO₄ modification, the ideal ratio of Pt dispersion to active site accessibility is reached as evidenced by the highest ECSA (15.38 m²/g Pt), the best mass activity (4.96 mA mg⁻¹ Pt), and the highest jgeo (8.04 mA cm⁻²) of Pt/15-CeVO₄/TiO₂. Furthermore, the diffusion coefficient of electron transfer is found to be 67.69×10−5 cm2s−1 under dark which is enhanced to 104.67×10−5 cm2s−1 for Pt/15-CeVO4/TiO2 under light. Noticeably, 15 SILAR layers of CeVO4 over TiO2 nanorods act as an efficient substrate of type-II heterojunction scheme to facilitate the methanol oxidation reaction activity of Pt potentially in Pt/15-CeVO4/TiO2 nanorods. Also, fluorescence spectra showed least electron/hole pair recombination with 15 SILAR layers of CeVO4 over TiO2 nanorods, evidencing the optimized penetration depth of electrons. Tuning CeVO4@1D TiO2 nanorods not only controlled solar spectrum sequestering but also contributed to decrease the Pt-CO bond strength via effective charge transfer in Pt/CeVO4/TiO2 by working as a cocatalyst. Such an interfacial engineering paved its way to explore other photocatalytic heterojunctions.

KW - 5-Scheme heterojunctions

KW - CO poisoning

KW - Effective charge transfer

KW - Interfacial engineering

KW - Interfacial interactions

KW - Noble metals

KW - Pt/CeVO/@TiO heterojunction

KW - S-scheme heterojunctions

KW - Type-II heterojunction

KW - Z-Scheme heterojunctions

UR - https://www.scopus.com/pages/publications/105005596992

U2 - 10.1016/j.molstruc.2025.142638

DO - 10.1016/j.molstruc.2025.142638

M3 - Article

AN - SCOPUS:105005596992

SN - 0022-2860

VL - 1342

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

M1 - 142638

ER -