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PdIn intermetallic nanoparticles for the hydrogenation of CO2 to methanol

Abstract:
Direct hydrogenation of CO2 to methanol could offer significant environmental benefits, if efficient catalysts can be developed. Here, bimetallic Pd-In nanoparticles show good performance as catalysts for this reaction. Unsupported nanoparticles are synthesised by the thermal decomposition of Pd(acetate)2 and In(acetate)3 precursors in a high boiling point solvent (squalane), followed by reduction using dilute H2 gas (210 °C). Adjusting the ratio of the two metallic precursors allow access to 5–10 nm nanoparticles with different phase compositions, including metallic Pd(0), In2O3 and intermetallic PdIn. Liquid phase methanol synthesis experiments (50 bar, 210 °C, H2:CO2 = 3:1) identify the intermetallic PdIn nanoparticles as the most efficient. The catalysts exhibit around 70% higher methanol rates (normalised to the overall molar metal content) compared to the conventional heterogeneous Cu/ZnO/Al2O3 catalyst (900 and 540 μmol mmolPdInorCuZnAl−1.h−1, respectively). In addition, the optimum Pd/In catalyst shows an improved methanol selectivity over the whole temperature range studied (190–270 °C), reaching >80% selectivity at 270 °C, compared to only 45% for the reference Cu/ZnO/Al2O3 catalyst. Experiments showed an improvement in stability; the methanol production rate declined by 20% after 120 h run for the optimum PdIn-based compared with 30% for the Cu/ZnO/Al2O3 catalyst (after 25 h). The optimum catalyst consists of ∼8 nm nanoparticles comprising a surface In-enriched PdIn intermetallic phase as characterised by XRD, HR-TEM, STEM-EDX and XPS. Post-catalysis analysis of the optimum catalyst shows that the same PdIn bimetallic phase is retained with only a slight increase in the nanoparticle size.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1016/j.apcatb.2017.07.069

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Role:
Author


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Grant:
EP/H046380, EP/K035274/1, EP/M013839/1, EP/M028291/1


Publisher:
Elsevier
Journal:
Applied Catalysis B: Environmental More from this journal
Volume:
220
Pages:
9-18
Publication date:
2017-07-25
Acceptance date:
2017-07-24
DOI:
ISSN:
0926-3373


Keywords:
Pubs id:
pubs:710885
UUID:
uuid:9f74005e-fda0-4445-a4cd-753a3c103554
Local pid:
pubs:710885
Source identifiers:
710885
Deposit date:
2017-08-07
ARK identifier:

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