Impact of doping ZrO2 with Sn on CO2 hydrogenation over dispersed Ru

Jiajia Zhao; Yuan Wang; Hamidreza Arandiyan; Anita M. D'Angelo; Aaron Seeber; Daksh Shah; Rachel A. Caruso; Ivan S. Cole; Yunxia Yang; Karen Wilson; Renata Lippi; Adam F. Lee

doi:10.1016/j.mtchem.2023.101665

Impact of doping ZrO₂ with Sn on CO₂ hydrogenation over dispersed Ru

Jiajia Zhao^*
, Yuan Wang
, Hamidreza Arandiyan
, Anita M. D'Angelo
, Aaron Seeber
, Daksh Shah
, Rachel A. Caruso
, Ivan S. Cole
, Yunxia Yang
, Karen Wilson
, Renata Lippi^*
, Adam F. Lee^*

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

Thermocatalytic CO₂ hydrogenation is a scalable route to renewable fuels and chemicals that can also mitigate climate change. Here, we demonstrate how subtle changes in a mixed phase zirconia support induce large changes in catalyst activity and selectivity. Ru/Sn_xZr_1-xO₂ catalysts were prepared using co-precipitated Sn-doped ZrO₂. Ru/ZrO₂ and Ru/Sn_0.01Zr_0.99O₂ both comprised tetragonal (t-) and monoclinic (m-) ZrO₂ nanoparticles decorated by RuO₂·H₂O clusters. Ru/Sn_0.2Zr_0.8O₂ exhibited similar textural properties and metal speciation, however, X-ray diffraction evidenced new crystalline phases wherein Sn atoms substituted for Zr. Operando XRD evidenced minimal perturbation of ZrO₂ and Sn-doped ZrO₂ phases, despite which 20 atom% Sn switched product selectivity from 99% CH₄ for Ru/ZrO₂ to 67% CO for Ru/Sn_0.2Zr_0.8O₂, due to increased support CO₂ adsorption capacity/strength. Operando infrared spectroscopy identify linear surface CO* as a catalytic spectator with (bi)carbonate a precursor to reactive HCOO*/carboxylate intermediates to methane. Sn_0.2Zr_0.8O₂ promotes CO₂/(bi)carbonate/formate decomposition, favouring a reverse water gas shift pathway.

Original language	English
Article number	101665
Journal	Materials Today Chemistry
Volume	32
DOIs	https://doi.org/10.1016/j.mtchem.2023.101665
Publication status	Published - Aug 2023
Externally published	Yes

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10.1016/j.mtchem.2023.101665

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@article{5663f792833c4073b8d03ee83ed910d5,

title = "Impact of doping ZrO2 with Sn on CO2 hydrogenation over dispersed Ru",

abstract = "Thermocatalytic CO2 hydrogenation is a scalable route to renewable fuels and chemicals that can also mitigate climate change. Here, we demonstrate how subtle changes in a mixed phase zirconia support induce large changes in catalyst activity and selectivity. Ru/SnxZr1-xO2 catalysts were prepared using co-precipitated Sn-doped ZrO2. Ru/ZrO2 and Ru/Sn0.01Zr0.99O2 both comprised tetragonal (t-) and monoclinic (m-) ZrO2 nanoparticles decorated by RuO2·H2O clusters. Ru/Sn0.2Zr0.8O2 exhibited similar textural properties and metal speciation, however, X-ray diffraction evidenced new crystalline phases wherein Sn atoms substituted for Zr. Operando XRD evidenced minimal perturbation of ZrO2 and Sn-doped ZrO2 phases, despite which 20 atom\% Sn switched product selectivity from 99\% CH4 for Ru/ZrO2 to 67\% CO for Ru/Sn0.2Zr0.8O2, due to increased support CO2 adsorption capacity/strength. Operando infrared spectroscopy identify linear surface CO* as a catalytic spectator with (bi)carbonate a precursor to reactive HCOO*/carboxylate intermediates to methane. Sn0.2Zr0.8O2 promotes CO2/(bi)carbonate/formate decomposition, favouring a reverse water gas shift pathway.",

keywords = "CO hydrogenation, Doping, Operando spectroscopy, Ruthenium, Zirconia",

author = "Jiajia Zhao and Yuan Wang and Hamidreza Arandiyan and D'Angelo, \{Anita M.\} and Aaron Seeber and Daksh Shah and Caruso, \{Rachel A.\} and Cole, \{Ivan S.\} and Yunxia Yang and Karen Wilson and Renata Lippi and Lee, \{Adam F.\}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors",

year = "2023",

month = aug,

doi = "10.1016/j.mtchem.2023.101665",

language = "English",

volume = "32",

journal = "Materials Today Chemistry",

issn = "2468-5194",

publisher = "Elsevier Ltd.",

}

TY - JOUR

T1 - Impact of doping ZrO2 with Sn on CO2 hydrogenation over dispersed Ru

AU - Zhao, Jiajia

AU - Wang, Yuan

AU - Arandiyan, Hamidreza

AU - D'Angelo, Anita M.

AU - Seeber, Aaron

AU - Shah, Daksh

AU - Caruso, Rachel A.

AU - Cole, Ivan S.

AU - Yang, Yunxia

AU - Wilson, Karen

AU - Lippi, Renata

AU - Lee, Adam F.

PY - 2023/8

Y1 - 2023/8

N2 - Thermocatalytic CO2 hydrogenation is a scalable route to renewable fuels and chemicals that can also mitigate climate change. Here, we demonstrate how subtle changes in a mixed phase zirconia support induce large changes in catalyst activity and selectivity. Ru/SnxZr1-xO2 catalysts were prepared using co-precipitated Sn-doped ZrO2. Ru/ZrO2 and Ru/Sn0.01Zr0.99O2 both comprised tetragonal (t-) and monoclinic (m-) ZrO2 nanoparticles decorated by RuO2·H2O clusters. Ru/Sn0.2Zr0.8O2 exhibited similar textural properties and metal speciation, however, X-ray diffraction evidenced new crystalline phases wherein Sn atoms substituted for Zr. Operando XRD evidenced minimal perturbation of ZrO2 and Sn-doped ZrO2 phases, despite which 20 atom% Sn switched product selectivity from 99% CH4 for Ru/ZrO2 to 67% CO for Ru/Sn0.2Zr0.8O2, due to increased support CO2 adsorption capacity/strength. Operando infrared spectroscopy identify linear surface CO* as a catalytic spectator with (bi)carbonate a precursor to reactive HCOO*/carboxylate intermediates to methane. Sn0.2Zr0.8O2 promotes CO2/(bi)carbonate/formate decomposition, favouring a reverse water gas shift pathway.

AB - Thermocatalytic CO2 hydrogenation is a scalable route to renewable fuels and chemicals that can also mitigate climate change. Here, we demonstrate how subtle changes in a mixed phase zirconia support induce large changes in catalyst activity and selectivity. Ru/SnxZr1-xO2 catalysts were prepared using co-precipitated Sn-doped ZrO2. Ru/ZrO2 and Ru/Sn0.01Zr0.99O2 both comprised tetragonal (t-) and monoclinic (m-) ZrO2 nanoparticles decorated by RuO2·H2O clusters. Ru/Sn0.2Zr0.8O2 exhibited similar textural properties and metal speciation, however, X-ray diffraction evidenced new crystalline phases wherein Sn atoms substituted for Zr. Operando XRD evidenced minimal perturbation of ZrO2 and Sn-doped ZrO2 phases, despite which 20 atom% Sn switched product selectivity from 99% CH4 for Ru/ZrO2 to 67% CO for Ru/Sn0.2Zr0.8O2, due to increased support CO2 adsorption capacity/strength. Operando infrared spectroscopy identify linear surface CO* as a catalytic spectator with (bi)carbonate a precursor to reactive HCOO*/carboxylate intermediates to methane. Sn0.2Zr0.8O2 promotes CO2/(bi)carbonate/formate decomposition, favouring a reverse water gas shift pathway.

KW - CO hydrogenation

KW - Doping

KW - Operando spectroscopy

KW - Ruthenium

KW - Zirconia

UR - https://www.scopus.com/pages/publications/85169825849

U2 - 10.1016/j.mtchem.2023.101665

DO - 10.1016/j.mtchem.2023.101665

M3 - Article

AN - SCOPUS:85169825849

SN - 2468-5194

VL - 32

JO - Materials Today Chemistry

JF - Materials Today Chemistry

M1 - 101665

ER -

Impact of doping ZrO₂ with Sn on CO₂ hydrogenation over dispersed Ru

Abstract

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