Surface modulation of CeO<sub>2</sub> by Nb doping to promote green synthesis of pentamethylene dicarbamate <italic style="font-style: italic">via</italic> carbonylation

Zhao Liyan; Wei Tiping; Zhang Jiajun; Hui Xiang; Guo Fengqin; Cao Yan; He Peng; Xu Shuang; Li Huiquan; Wang Liguo

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Surface modulation of CeO₂ by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation

Updated：2026-08-24

- Surface modulation of CeO₂ by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation
- Chinese Journal of Chemical Engineering Vol. 94, Issue 6, Pages: 172-184(2026)
- Affiliations：
  
  National Engineering Research Center of Green Recycling for Strategic Metal Resources, Beijing 100190, China
  School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
- Author bio：
  
  Corresponding authors. E-mail addresses: hqli@ipe.ac.cn(H. Li)
  lgwang@ipe.ac.cn(L. Wang)
- Funds：
- DOI：
  CLC：
- Received：16 October 2025，
  
  Revised：2025-12-24，
  
  Accepted：26 December 2025，
  
  Online First：19 February 2026，
  
  Published：2026-06
- Accepted：
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Zhao Liyan, Wei Tiping, Zhang Jiajun, et al. Surface modulation of CeO₂ by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation[J]. Chinese Journal of Chemical Engineering, 2026, 94(6): 172-184.
DOI：

Zhao Liyan, Wei Tiping, Zhang Jiajun, et al. Surface modulation of CeO₂ by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation[J]. Chinese Journal of Chemical Engineering, 2026, 94(6): 172-184. DOI：

摘要

Abstract

Bio-based pentamethylene dicarbamate (PDC) serves as a crucial intermediate in the synthesis of biobased pentamethylene diisocyanate (PDI)

via

a non-phosgene route

and its carbonylation synthesis holds significant scientific and industrial importance. In this study

niobium-doped ceria (Nb

Ce) catalysts were designed and synthesized for the carbonylation reaction between pentanediamine (PDA) and methyl carbamate (MC). The catalytic performance of CeO

on the carbonylation of PDA was promoted by the surface modulation by Nb doping. Nb

0.06

Ce achieved a space-time yield of PDC up to 32.4 g PDC·(g cat.)

-1

·h

- 1

which was 1.4 times higher than that of CeO

. The catalysts were characterized by XRD

BET

TEM

XPS

EPR

/CO

-TPD

and Py-IR. Catalyst characterization results suggested that the superior catalytic performance of Nb

0.06

Ce may be attributed to the synergistic combination of high oxygen vacancy concentration

abundant surface-adsorbed oxygen species

plentiful acid-base sites

and a large specifi

c surface area.

In-situ

FTIR analysis confirmed that the alcoholysis of polyurea intermediates was a key step in the synthesis of PDC

and this process was notably accelerated in the presence of the catalyst.

In-situ

DRIFTS further indicated the Nb

0.06

Ce facilitated the adsorption and activation of reactants. In the catalytic reaction

the polyurea intermediate was activated by the acidbase sites on the surface of Nb

generating the final product PDC. The Nb

0.06

Ce catalyst demonstrated excellent stability

maintaining its catalytic activity after multiple reaction cycles. Furthermore

it was successfully applied to the efficient carbonylation synthesis of various aliphatic carbamates

highlighting its broad applicability.

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Keywords

references

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⁰

Surface modulation of CeO2 by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation

DOI：

摘要

Abstract

关键词

Keywords

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Surface modulation of CeO₂ by Nb doping to promote green synthesis of pentamethylene dicarbamate via carbonylation