Aqueous-Phase Reforming of Methanol for Hydrogen Production on Nitrogen-Doped Ceria: The Effect of the Doping Method

Songqi Leng; Taizong Shen; Shuting Li; Haoyu Wang; Shahzad Barghi; Dan Wu; Chunbao Charles Xu

doi:10.1021/acssuschemeng.5c02140

Aqueous-Phase Reforming of Methanol for Hydrogen Production on Nitrogen-Doped Ceria: The Effect of the Doping Method

Songqi Leng
, Taizong Shen
, Shuting Li
, Haoyu Wang
, Shahzad Barghi^*
, Dan Wu
, Chunbao Charles Xu^*

^*Corresponding author for this work

School of Energy and Environment

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

8 Citations (Scopus)

Abstract

This study first compares the effects of three nitrogen doping methods, namely, solvothermal, hydrothermal, and coheat treatments, on the catalytic performance of Pt/CeO₂ catalysts for aqueous-phase reforming (APR) of methanol to produce hydrogen. Characterization techniques (X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), temperature-programmed desorption of O₂ (O₂-TPD), and Fourier transform infrared spectroscopy (FT-IR)) were used to analyze the impact of the N-dopant type and content on oxygen vacancy formation, Ce³⁺ ratio, crystal structure, and active sites. Compared to the undoped sample, N-doping significantly enhanced the catalytic performance, increasing the turnover frequency (TOF) from 773 to 1290/h at 200 °C with 0.5 wt % Pt and a methanol-to-water molar ratio of 1:1. Hydrothermal treatment generated more oxygen vacancies due to Ce-N-O bond formation, while coheat treatment produced both Ce-N-O and Ce-N bonds. Triethanolamine (TEA) proved effective for hydrothermal N-doping, promoting oxygen vacancies via ethanol derivative formation. In contrast, solvothermal treatment was less effective due to inadequate N-doping and disruption of the CeO₂ nanorods. This study highlights the importance of selecting suitable N-doping strategies to improve the activity and stability of Pt/CeO₂ catalysts for hydrogen production. © 2025 American Chemical Society.

Original language	English
Pages (from-to)	8078-8092
Journal	ACS Sustainable Chemistry & Engineering
Volume	13
Issue number	21
Online published	21 May 2025
DOIs	https://doi.org/10.1021/acssuschemeng.5c02140
Publication status	Published - 2 Jun 2025

Funding

The authors are grateful for the financial support from the Natural Science and Engineering Research Council of Canada (NSERC) via Discovery Grant and the Start-up grant from City University of Hong Kong, as well as a scholarship offered to one of the authors (S.Leng) from China Scholarship Council (CSC No. 202206820010).

UN SDGs

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

SDG 7 Affordable and Clean Energy

Research Keywords

hydrogen economy
hydrothermal assisted N-doping
low CO selectivity
oxygen vacancy
Pt/CeO2 catalyst

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@article{2a92d84f130a4cf49229db3390b4971c,

title = "Aqueous-Phase Reforming of Methanol for Hydrogen Production on Nitrogen-Doped Ceria: The Effect of the Doping Method",

abstract = "This study first compares the effects of three nitrogen doping methods, namely, solvothermal, hydrothermal, and coheat treatments, on the catalytic performance of Pt/CeO2 catalysts for aqueous-phase reforming (APR) of methanol to produce hydrogen. Characterization techniques (X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), temperature-programmed desorption of O2 (O2-TPD), and Fourier transform infrared spectroscopy (FT-IR)) were used to analyze the impact of the N-dopant type and content on oxygen vacancy formation, Ce3+ ratio, crystal structure, and active sites. Compared to the undoped sample, N-doping significantly enhanced the catalytic performance, increasing the turnover frequency (TOF) from 773 to 1290/h at 200 °C with 0.5 wt \% Pt and a methanol-to-water molar ratio of 1:1. Hydrothermal treatment generated more oxygen vacancies due to Ce-N-O bond formation, while coheat treatment produced both Ce-N-O and Ce-N bonds. Triethanolamine (TEA) proved effective for hydrothermal N-doping, promoting oxygen vacancies via ethanol derivative formation. In contrast, solvothermal treatment was less effective due to inadequate N-doping and disruption of the CeO2 nanorods. This study highlights the importance of selecting suitable N-doping strategies to improve the activity and stability of Pt/CeO2 catalysts for hydrogen production. {\textcopyright} 2025 American Chemical Society.",

keywords = "hydrogen economy, hydrothermal assisted N-doping, low CO selectivity, oxygen vacancy, Pt/CeO2 catalyst",

author = "Songqi Leng and Taizong Shen and Shuting Li and Haoyu Wang and Shahzad Barghi and Dan Wu and Xu, \{Chunbao Charles\}",

year = "2025",

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doi = "10.1021/acssuschemeng.5c02140",

language = "English",

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journal = "ACS Sustainable Chemistry \& Engineering",

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TY - JOUR

T1 - Aqueous-Phase Reforming of Methanol for Hydrogen Production on Nitrogen-Doped Ceria

T2 - The Effect of the Doping Method

AU - Leng, Songqi

AU - Shen, Taizong

AU - Li, Shuting

AU - Wang, Haoyu

AU - Barghi, Shahzad

AU - Wu, Dan

AU - Xu, Chunbao Charles

PY - 2025/6/2

Y1 - 2025/6/2

N2 - This study first compares the effects of three nitrogen doping methods, namely, solvothermal, hydrothermal, and coheat treatments, on the catalytic performance of Pt/CeO2 catalysts for aqueous-phase reforming (APR) of methanol to produce hydrogen. Characterization techniques (X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), temperature-programmed desorption of O2 (O2-TPD), and Fourier transform infrared spectroscopy (FT-IR)) were used to analyze the impact of the N-dopant type and content on oxygen vacancy formation, Ce3+ ratio, crystal structure, and active sites. Compared to the undoped sample, N-doping significantly enhanced the catalytic performance, increasing the turnover frequency (TOF) from 773 to 1290/h at 200 °C with 0.5 wt % Pt and a methanol-to-water molar ratio of 1:1. Hydrothermal treatment generated more oxygen vacancies due to Ce-N-O bond formation, while coheat treatment produced both Ce-N-O and Ce-N bonds. Triethanolamine (TEA) proved effective for hydrothermal N-doping, promoting oxygen vacancies via ethanol derivative formation. In contrast, solvothermal treatment was less effective due to inadequate N-doping and disruption of the CeO2 nanorods. This study highlights the importance of selecting suitable N-doping strategies to improve the activity and stability of Pt/CeO2 catalysts for hydrogen production. © 2025 American Chemical Society.

AB - This study first compares the effects of three nitrogen doping methods, namely, solvothermal, hydrothermal, and coheat treatments, on the catalytic performance of Pt/CeO2 catalysts for aqueous-phase reforming (APR) of methanol to produce hydrogen. Characterization techniques (X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), temperature-programmed desorption of O2 (O2-TPD), and Fourier transform infrared spectroscopy (FT-IR)) were used to analyze the impact of the N-dopant type and content on oxygen vacancy formation, Ce3+ ratio, crystal structure, and active sites. Compared to the undoped sample, N-doping significantly enhanced the catalytic performance, increasing the turnover frequency (TOF) from 773 to 1290/h at 200 °C with 0.5 wt % Pt and a methanol-to-water molar ratio of 1:1. Hydrothermal treatment generated more oxygen vacancies due to Ce-N-O bond formation, while coheat treatment produced both Ce-N-O and Ce-N bonds. Triethanolamine (TEA) proved effective for hydrothermal N-doping, promoting oxygen vacancies via ethanol derivative formation. In contrast, solvothermal treatment was less effective due to inadequate N-doping and disruption of the CeO2 nanorods. This study highlights the importance of selecting suitable N-doping strategies to improve the activity and stability of Pt/CeO2 catalysts for hydrogen production. © 2025 American Chemical Society.

KW - hydrogen economy

KW - hydrothermal assisted N-doping

KW - low CO selectivity

KW - oxygen vacancy

KW - Pt/CeO2 catalyst

UR - https://www.scopus.com/pages/publications/105005755460

UR - https://www.scopus.com/pages/publications/105005755460#tab=impact

U2 - 10.1021/acssuschemeng.5c02140

DO - 10.1021/acssuschemeng.5c02140

M3 - RGC 21 - Publication in refereed journal

SN - 2168-0485

VL - 13

SP - 8078

EP - 8092

JO - ACS Sustainable Chemistry & Engineering

JF - ACS Sustainable Chemistry & Engineering

IS - 21

ER -

Aqueous-Phase Reforming of Methanol for Hydrogen Production on Nitrogen-Doped Ceria: The Effect of the Doping Method

Abstract

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UN SDGs

Research Keywords

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