Mechanochemical Effect in Mixing Sponge Copper with Amorphous ZrO<sub>2</sub>Creates Effective Active Sites for Methanol Synthesis by CO<sub>2</sub>Hydrogenation

Oshima, Kazumasa; Honma, Yuka; Kinoshita, Kazuya; Gao, Zhiming; Honma, Tetsuo; Tada, Shohei; Satokawa, Shigeo

doi:10.1021/acs.jpcc.0c10917

Cited by 11 publications

(6 citation statements)

References 46 publications

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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%

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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Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…3,4 One of the most important applications is methanol synthesis by CO 2 hydrogenation for the reuse of CO 2 to reduce greenhouse gas emissions. To control the absorption and reactivity of CO 2 , morphology dependence is crucial, 1,5,6 and experimental preparations can control the morphology of zirconia. For example, the dehydration of amorphous (am)-Zr(OH) 4 results in amorphous zirconia (am-ZrO 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…Zirconium oxides, ZrO 2 , and zirconium hydroxides, Zr(OH) 4 , also called hydrous zirconia, are important materials for various scientific and industrial applications, such as catalysts , and adsorbents. , One of the most important applications is methanol synthesis by CO 2 hydrogenation for the reuse of CO 2 to reduce greenhouse gas emissions. To control the absorption and reactivity of CO 2 , morphology dependence is crucial, ,, and experimental preparations can control the morphology of zirconia. For example, the dehydration of amorphous ( am )-Zr(OH) 4 results in amorphous zirconia ( am -ZrO 2 ).…”

Section: Introductionmentioning

confidence: 99%

Adsorption of CO₂ on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

Joutsuka

Tada

2023

J. Phys. Chem. C

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Herein, we study the structural and electronic origins of molecular adsorption using experiments and density functional theory (DFT) calculations. We performed X-ray diffraction (XRD) and temperature-programmed desorption (TPD) of CO2 on amorphous zirconia (am-ZrO2) and crystalline (tetragonal and monoclinic) zirconia. Using molecular dynamics simulations, the bulk structures of am-ZrO2 and am-zirconium(IV) hydroxide (am-Zr(OH)4) were obtained and the reproducibility of the experimental structure was confirmed by comparing the radial distribution functions. In addition, the hydroxyl density on the hydrogenated ZrO2 surfaces was found to be consistent with the experimental results. Both experiments and simulations indicate that the adsorption of CO2 on an am-ZrO2 surface is more heterogeneous and weaker than that on a crystalline zirconia surface. Because the charge environment and band structures of crystalline zirconia are approximately the same as those of am-ZrO2, the weak adsorption on the am-ZrO2 surface arises from the fewer and stronger Zr–O bonds on the surface. These findings provide molecular-level insight not only for the adsorption of CO2 but also into the molecular adsorption on ZrO2-based catalysts.

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“…3,4 One of the most important applications is methanol synthesis by CO2 hydrogenation for the reuse of CO2 to reduce greenhouse gas emissions. To control the absorption and reactivity of CO2, morphology dependence is crucial, 1,5,6 and experimental preparations can control the morphology of zirconia. For example, the dehydration of amorphous (am)-Zr(OH)4 results in amorphous zirconia (am-ZrO2).…”

Section: Introductionmentioning

confidence: 99%

Adsorption of CO2 on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

Joutsuka

Tada²

2023

Preprint

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Herein, we study the structural and electronic origins of molecular adsorption using experiments and density functional theory (DFT) calculations. We performed X-ray diffraction (XRD) and temperature-programmed desorption (TPD) of CO2 on amorphous zirconia (am-ZrO2) and crystalline (tetragonal and monoclinic) zirconia. Using molecular dynamics simulations, the bulk structures of am-ZrO2 and am-zirconium(IV) hydroxide (am-Zr(OH)4) were obtained and the reproducibility of the experimental structure was confirmed by comparing the radial distribution functions. In addition, the hydroxyl density on the hydrogenated ZrO2 surfaces was found to be consistent with the experimental results. Both experiments and simulations indicate that the adsorption of CO2 on an am-ZrO2 surface is more heterogeneous and weaker than that on a crystalline zirconia surface. Because the charge environment and band structures of crystalline zirconia are approximately the same as those of am-ZrO2, the weak adsorption on the am-ZrO2 surface arises from the fewer and stronger Zr-O bonds on the surface. These findings provide molecular-level insight not only for the adsorption of CO2 but also into the molecular adsorption on ZrO2-based catalysts.

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Mechanochemical Effect in Mixing Sponge Copper with Amorphous ZrO₂Creates Effective Active Sites for Methanol Synthesis by CO₂Hydrogenation

Cited by 11 publications

References 46 publications

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

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

Adsorption of CO₂ on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

Adsorption of CO2 on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

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Mechanochemical Effect in Mixing Sponge Copper with Amorphous ZrO2Creates Effective Active Sites for Methanol Synthesis by CO2Hydrogenation

Cited by 11 publications

References 46 publications

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

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

Adsorption of CO2 on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

Adsorption of CO2 on Amorphous and Crystalline Zirconia: A DFT and Experimental Study

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Mechanochemical Effect in Mixing Sponge Copper with Amorphous ZrO₂Creates Effective Active Sites for Methanol Synthesis by CO₂Hydrogenation

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

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

Adsorption of CO₂ on Amorphous and Crystalline Zirconia: A DFT and Experimental Study