Reactivity of a Zirconia–Copper Inverse Catalyst for CO<sub>2</sub> Hydrogenation

Ma, Yeming; Wang, Jason; Goodman, Kenneth R.; Head, Ashley R.; Tong, Xiao; Stacchiola, Darı́o; White, Michael G.

doi:10.1021/acs.jpcc.0c06624

Cited by 48 publications

(52 citation statements)

References 117 publications

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“…In Figure 2(a), the Zr 3d binding energies match those found before for ZrO 2 nanoparticles in contact with the Cu x O/Cu(111) substrate. 26,27 The presence of the copper oxide under the ZrO 2 affects the relaxation of the Zr 3d core holes in XPS. 26,27 Once the copper oxide is removed by reaction with hydrogen, the Zr 3d binding energies for ZrO 2 /Cu(111) shift to positions which are very close to the range of values reported for tetragonal and monoclinic ZrO 2 , 33 with the O/Zr atomic ratio being very close to 2.…”

Section: ■ Methodsmentioning

confidence: 99%

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Rui

Gutiérrez

Rosales

et al. 2021

Ind. Eng. Chem. Res.

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The conversion and utilization of carbon dioxide is a critical challenge for the reduction of greenhouse gas pollution and in the production of high value chemicals in C1 chemistry. ZrO2/Cu(111) is an inverse oxide/metal catalyst that displays high activity and stability for the hydrogenation of CO2 into methanol at 500–600 K. At elevated temperatures, ZrO2 grows on a CuO x /Cu(111) substrate forming islands of 10–12 nm in size and an average height of ∼3 Å. Reaction with H2 leads to the removal of the copper oxide producing ZrO2/Cu(111) surfaces which are very active for the binding and dissociation of CO2 into CO and C. After exposing ZrO2/Cu(111) to moderate or elevated pressures of a CO2/H2 mixture at 300 K, atomic C and minor amounts of CH x O and CO x are deposited on the catalyst surface. The adsorbed CH x O and CO x disappear upon heating above 400 K. The catalytic tests for CO2 hydrogenation give CO as the main reaction product and CH4 and CH3OH as secondary products. The relative yields of methane and methanol change with time and track the amount of atomic C deposited on the active ZrO2/Cu(111) surface. The formation of methane stops once the catalyst surface is saturated with C. Under steady-state conditions, ZrO2/Cu(111) is a much better catalyst for methanol synthesis than ZnO/Cu(111). This trend reflects variations in the size of the oxide islands and in the strength of oxide-metal interactions. The use of an inverse oxide/metal configuration is an important synthetic tool when preparing active, selective, and stable catalysts for CO2 hydrogenation.

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Section: ■ Methodsmentioning

confidence: 99%

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Rui

Gutiérrez

Rosales

et al. 2021

Ind. Eng. Chem. Res.

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“…In other words, the methanol production rate only from CO 2 and H 2 is much less than that from CO/CO 2 /H 2 . Therefore, a significant number of studies have been carried out to develop prospective catalysts specific toward CO 2 -to-methanol hydrogenation, such as In 2 O 3 /ZrO 2 , Pd/In 2 O 3 , Pd/SiO 2 , Pd/ZnO, Pt/MoO x /TiO 2 , Re/TiO 2 , Cu/ZnO/graphene, Cu/Al/Zn/Zr (hydrotalcite), , Cu/TiO 2 , Cu/ZnO/ZrO 2 , , Cu/ZrO 2 , − and Cu/AlCeO . Cu catalysts selectively produce oxygenates ( e.g.…”

Section: Introductionmentioning

confidence: 99%

“…We have focused on Cu/ZrO 2 because it has both activity and selectivity toward CO 2 -to-methanol hydrogenation. − The reaction mechanism over Cu/ZrO 2 has been thought to be as follows (Figure ): CO 2 and H 2 adsorb on ZrO 2 and Cu, respectively (adsorption step, eq ), , and then CO 2 reacts with H 2 to form methanol at Cu-ZrO 2 interfacial sites (reaction step). Other papers have also reported the importance of the interface. , In parallel to the reaction step, CO 2 reacts with H 2 to form CO (reverse water gas shift reaction, eq ). − In addition, the produced methanol is decomposed to CO to some extent (decomposition step, eq ).…”

Section: Introductionmentioning

confidence: 99%

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Effect of Sm Doping on CO₂-to-Methanol Hydrogenation of Cu/Amorphous-ZrO₂ Catalysts

et al. 2021

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A series of 14 wt % Cu/Sm2O3/a-ZrO2 (a-: amorphous) catalysts for CO2-to-methanol hydrogenation were prepared by a coimpregnation method. When the Sm loading was 5–6 mol %, the CO2 conversion reached the maximum value (10.1% for 5 mol % catalyst and 9.4% for 6 mol % catalyst). In contrast, methanol selectivity decreased monotonically from 79% to 67% as the Sm loading increased from 0 to 7 mol %. Among the prepared catalysts, the 5–6 mol % Sm-doped Cu/a-ZrO2 catalyst exhibited the highest methanol production rate of 3.7 mmol gcat –1 h–1, which was ca. 20% greater than that with no Sm dopant (3.1 mmol gcat –1 h–1), at 1.0 MPa and 230 °C with a space velocity = 6 L(STP) gcat –1 h–1. When we took into consideration the results of temperature-programmed reduction by H2, X-ray diffraction, and X-ray photoelectron spectroscopy, doping Sm species into Cu/a-ZrO2 increased the number of surface-dispersed Cu2+, resulting in the high dispersion of Cu nanoparticles, as well as an increase in the number of the active sites (interfacial sites between Cu and a-ZrO2). Furthermore, according to the temperature-programmed desorption of CO2, Sm doping promoted CO2 adsorption on the catalysts and simultaneously activated CO2. The negative effect of Sm doping is a drop in methanol selectivity. In other words, it results in an improvement in methanol decomposition to CO. An excess amount of Sm led to Cu sintering. The main active sites (Cu-ZrO2 interface) are expected to be destroyed by sintering the Cu particles, in other words, losing the interaction between Cu and a-ZrO2. Therefore, since the above-mentioned positive effect and negative effect coexist, there is an optimum value for the amount of Sm doping.

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“…Generalizing the relationship between surface characteristics and ensemble size is further complicated by metal oxide clusters on metal surfaces. While we often think of effective thermal catalysts as metal clusters on oxide surfaces, "inverse" catalysts have shown excellent performance 62 , being as or more reactive in CO 2 reduction to methanol, [63][64][65] as well as the water-gas shift reaction (WGSR), 66,67 and CO oxidation. 68 These systems are also of interest for giving insight into their "non-inverse" counterparts as, unlike irreducible metal oxides, metal surfaces allow for use of photoemission, ion scattering, and other charged-particle probes of atomic composition and electronic structure.…”

Section: Surfaces and Supportsmentioning

confidence: 99%

Ensemble representation of catalytic interfaces: soloists, orchestras, and everything in-between

Lavroff

Morgan

Zhang

et al. 2022

Preprint

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Catalytic systems are complex and dynamic, exploring vast chemical spaces on multiple timescales. In this perspective, we discuss the dynamic behavior of heterogeneous thermal and electrocatalysts and the ensembles of many isomers which govern their behavior. We develop a new paradigm in catalysis theory in which highly fluxional systems, such as supported sub-nano clusters, isomerize on a much shorter timescale than that of the catalyzed reaction, so macroscopic properties arise from the thermal ensemble of isomers, not just the ground state. Accurate chemical predictions can only be reached through a many-structure picture of the catalyst, and we explain the breakdown of conventional methods such as linear scaling relations and size-selected prevention of sintering. We capitalize on the forward-looking discussion of the means of controlling the size of these dynamic ensembles. This control, such that the most effective or selective isomers can dominate the system, is essential for the fluxional catalyst to be practicable, and their targeted synthesis to be possible. It will also provide a fundamental lever of catalyst design. Finally, we discuss computational tools and experimental methods for probing ensembles and the role of specific isomers. We hope that catalyst optimization using chemically informed descriptors of ensemble nature and size will become a new norm in the field of catalysis and have broad impacts in sustainable energy, efficient chemical production, and more.

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Reactivity of a Zirconia–Copper Inverse Catalyst for CO₂ Hydrogenation

Cited by 48 publications

References 117 publications

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Effect of Sm Doping on CO₂-to-Methanol Hydrogenation of Cu/Amorphous-ZrO₂ Catalysts

Ensemble representation of catalytic interfaces: soloists, orchestras, and everything in-between

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Reactivity of a Zirconia–Copper Inverse Catalyst for CO2 Hydrogenation

Cited by 48 publications

References 117 publications

CO2 Hydrogenation on ZrO2/Cu(111) Surfaces: Production of Methane and Methanol

CO2 Hydrogenation on ZrO2/Cu(111) Surfaces: Production of Methane and Methanol

Effect of Sm Doping on CO2-to-Methanol Hydrogenation of Cu/Amorphous-ZrO2 Catalysts

Ensemble representation of catalytic interfaces: soloists, orchestras, and everything in-between

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Reactivity of a Zirconia–Copper Inverse Catalyst for CO₂ Hydrogenation

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

CO₂ Hydrogenation on ZrO₂/Cu(111) Surfaces: Production of Methane and Methanol

Effect of Sm Doping on CO₂-to-Methanol Hydrogenation of Cu/Amorphous-ZrO₂ Catalysts