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Green and scalable approaches for synthesis and encapsulating clean metal nanoclusters inside cerium MOFs for efficient glycerol carboxylation with CO2

Lukato, Simon ; Krogul-Sobczak, Agnieszka ; Litwinienko, Grzegorz ; Wendt, Ola F. LU ; Wallenberg, Reine LU ; Hallböök, Filip LU orcid and Wojcik, Michal (2025) In Journal of CO2 Utilization 102.
Abstract

In the pursuit of CO₂-neutral renewable energy solutions, biofuels have emerged as one of the key strategies. However, biodiesel production generates a surplus of crude glycerol (GL), creating a need for efficient valorization pathways. The conversion of GL into value-added chemicals represents a sustainable approach to address this issue. Metal nanoclusters (NCats) embedded within metal-organic frameworks (MOFs) constitute a promising class of hybrid catalysts for GL–CO₂ coupling, yet their controlled synthesis remains limited to a few MOF systems. Herein, we present a clean, scalable, and efficient method for the synthesis of ultra-small, surfactant-free Cu, Ag, and Pd NCats encapsulated in cerium-based MOFs. The resulting catalysts... (More)

In the pursuit of CO₂-neutral renewable energy solutions, biofuels have emerged as one of the key strategies. However, biodiesel production generates a surplus of crude glycerol (GL), creating a need for efficient valorization pathways. The conversion of GL into value-added chemicals represents a sustainable approach to address this issue. Metal nanoclusters (NCats) embedded within metal-organic frameworks (MOFs) constitute a promising class of hybrid catalysts for GL–CO₂ coupling, yet their controlled synthesis remains limited to a few MOF systems. Herein, we present a clean, scalable, and efficient method for the synthesis of ultra-small, surfactant-free Cu, Ag, and Pd NCats encapsulated in cerium-based MOFs. The resulting catalysts were evaluated in the direct carboxylation of crude GL with CO₂. Among them, the Pd₁Cu₁@MOF1 composite demonstrated outstanding performance, achieving > 73 % yield and a TOF > 100 h⁻¹ with pure GL, and > 14 % yield with a TOF of 30 h⁻¹ using crude GL. The method also enabled successful incorporation of trimetallic PdAgCu NCats, highlighting its potential for the sustainable synthesis of multimetallic NCats-MOF catalytic systems.

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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Bio-glycerol, Carboxylation, CO, Crude, Nanoclusters-MOFs
in
Journal of CO2 Utilization
volume
102
article number
103243
publisher
Elsevier
external identifiers
  • scopus:105020572528
ISSN
2212-9820
DOI
10.1016/j.jcou.2025.103243
language
English
LU publication?
yes
id
a0d8559c-1e12-468d-8e8b-370063d1e6ad
date added to LUP
2025-12-10 09:19:25
date last changed
2025-12-10 09:19:25
@article{a0d8559c-1e12-468d-8e8b-370063d1e6ad,
  abstract     = {{<p>In the pursuit of CO₂-neutral renewable energy solutions, biofuels have emerged as one of the key strategies. However, biodiesel production generates a surplus of crude glycerol (GL), creating a need for efficient valorization pathways. The conversion of GL into value-added chemicals represents a sustainable approach to address this issue. Metal nanoclusters (NCats) embedded within metal-organic frameworks (MOFs) constitute a promising class of hybrid catalysts for GL–CO₂ coupling, yet their controlled synthesis remains limited to a few MOF systems. Herein, we present a clean, scalable, and efficient method for the synthesis of ultra-small, surfactant-free Cu, Ag, and Pd NCats encapsulated in cerium-based MOFs. The resulting catalysts were evaluated in the direct carboxylation of crude GL with CO₂. Among them, the Pd₁Cu₁@MOF1 composite demonstrated outstanding performance, achieving &amp;gt; 73 % yield and a TOF &amp;gt; 100 h⁻¹ with pure GL, and &amp;gt; 14 % yield with a TOF of 30 h⁻¹ using crude GL. The method also enabled successful incorporation of trimetallic PdAgCu NCats, highlighting its potential for the sustainable synthesis of multimetallic NCats-MOF catalytic systems.</p>}},
  author       = {{Lukato, Simon and Krogul-Sobczak, Agnieszka and Litwinienko, Grzegorz and Wendt, Ola F. and Wallenberg, Reine and Hallböök, Filip and Wojcik, Michal}},
  issn         = {{2212-9820}},
  keywords     = {{Bio-glycerol; Carboxylation; CO; Crude; Nanoclusters-MOFs}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Journal of CO2 Utilization}},
  title        = {{Green and scalable approaches for synthesis and encapsulating clean metal nanoclusters inside cerium MOFs for efficient glycerol carboxylation with CO<sub>2</sub>}},
  url          = {{http://dx.doi.org/10.1016/j.jcou.2025.103243}},
  doi          = {{10.1016/j.jcou.2025.103243}},
  volume       = {{102}},
  year         = {{2025}},
}