Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support

Aitor Arandia; Jorge A. Velasco; Ahmed Sajid; Jihong Yim; Hammad Shamshad; Hua Jiang; Ashish Chahal; Abhinash Kumar Singh; Christine Gonsalves; Reetta Karinen; Riikka L. Puurunen

doi:10.1016/j.cattod.2025.115283

Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support

Aitor Arandia, Jorge A. Velasco, Ahmed Sajid, Jihong Yim, Hammad Shamshad, Hua Jiang, Ashish Chahal, Abhinash Kumar Singh, Christine Gonsalves, Reetta Karinen, Riikka L. Puurunen^*

^*Corresponding author for this work

BA5208 Catalytic processes

Aalto University

Research output: Contribution to journal › Article › Scientific › peer-review

Abstract

Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.

Original language	English
Article number	115283
Journal	Catalysis Today
Volume	454
DOIs	https://doi.org/10.1016/j.cattod.2025.115283
Publication status	Published - 15 Jun 2025
MoE publication type	A1 Journal article-refereed

Funding

The work at Aalto University was financially supported by the Research Council of Finland (RCF, formerly Academy of Finland), COOLCAT consortium, decision no. 329978, and ALDI consortium, decision no. 331082. Purchasing the AutoChem III tool was supported by RCF calls FIRI 2018, grant no. 319467, and FIRI 2019, grant no. 327865.

Keywords

Atomic layer deposition
Carbon dioxide
Copper
Hydrogenation
Methanol
Zinc oxide

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title = "Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support",

abstract = "Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.",

keywords = "Atomic layer deposition, Carbon dioxide, Copper, Hydrogenation, Methanol, Zinc oxide",

author = "Aitor Arandia and Velasco, {Jorge A.} and Ahmed Sajid and Jihong Yim and Hammad Shamshad and Hua Jiang and Ashish Chahal and Singh, {Abhinash Kumar} and Christine Gonsalves and Reetta Karinen and Puurunen, {Riikka L.}",

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T1 - Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol

T2 - Influence of support

AU - Arandia, Aitor

AU - Velasco, Jorge A.

AU - Sajid, Ahmed

AU - Yim, Jihong

AU - Shamshad, Hammad

AU - Jiang, Hua

AU - Chahal, Ashish

AU - Singh, Abhinash Kumar

AU - Gonsalves, Christine

AU - Karinen, Reetta

AU - Puurunen, Riikka L.

PY - 2025/6/15

Y1 - 2025/6/15

N2 - Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.

AB - Copper promoted with zinc is an active catalyst for carbon dioxide hydrogenation to methanol, a reaction relevant to carbon capture and utilization technologies. Previous work showed that inverse zinc-on-copper catalysts on zirconia supports, where zinc(II) is added via atomic layer deposition (ALD), are more active and selective in this reaction than copper-on-zinc catalysts on zirconia. This work continues exploring the inverse zinc-on-copper catalysts by varying the support, comparing zirconia support with alumina, titania and niobia, and with various combinations of the ceria-zirconia-lanthana mixed oxide family. Catalyst characterization was made with elemental analysis, temperature-programmed reduction, temperature-programmed desorption of carbon dioxide, nitrous oxide pulse titration, and transmission electron microscopy. Activity was measured in a fixed-bed flow reactor at 450–550 K. ALD of Zn(II) acetylacetonate gave a similar areal number density of ca. two zinc per square nanometer on all tested supports. Zinc promotion systematically increased the methanol production rate. Among the tested catalysts, the zinc-on-copper on zirconia support remained the most active, with other catalysts from the ceria-zirconia-lanthana mixed oxide family giving almost as good results.

KW - Atomic layer deposition

KW - Carbon dioxide

KW - Copper

KW - Hydrogenation

KW - Methanol

KW - Zinc oxide

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VL - 454

JO - Catalysis Today

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Atomic layer deposited zinc promoted copper catalysts for carbon dioxide hydrogenation to methanol: Influence of support

Abstract

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Keywords

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