Highly Efficient CuPd_0.1/γ-Al₂O₃ Catalyst with Isolated Pd Species for CO₂ Hydrogenation to Methanol

Abstract

CO2 hydrogenation is one of the most effective solutions for mitigating excessive CO2 emissions. In this work, CuPd x /γ-Al2O3 (x = 0.05–5.7 wt %) catalysts were prepared and applied in CO2 hydrogenation to methanol. The results showed CuPd0.1/γ-Al2O3 achieved excellent CO2 hydrogenation activity. It is demonstrated that the Pd species of CuPd0.1/γ-Al2O3 is highly dispersed on the γ-Al2O3 support at the atomic level and separated from Cu nanoparticles by AC-HAADF-STEM, rather than forming CuPd alloy. Part of the hydrogen species activated by isolated Pd atoms overflows onto γ-Al2O3 and influences the reduction of CuO, thus effectively increasing the Cu+/(Cu++Cu0) ratio which is correlated with the prominent CO2 hydrogenation performance. On the other hand, we found that CH3OH retained on catalyst surface can be further reformed into CO, which significantly reduces the selectivity of CH3OH. To limit CH3OH reforming, the activity test of CuPd0.1/γ-Al2O3 in a fixed bed at different weight hourly space velocity was performed, where the remarkable methanol yields of 5.9 mmol/gcat./h were obtained.

Synergistic nanoalloy PdCu/TiO 2 catalyst for in situ hydrogenation of biomass-derived furfural at room temperature

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 μmol g −1 , entry 4, Table S2, ESI†) is intermediate between the Pd/TiO 2 and Cu/TiO 2 catalysts (10.40 and 22.54 μmol g −1 , respectively, entries 2 and 3, Table S2, ESI†), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd–Cu alloy. 82,83…”

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 µmol g −1 , entry 4, Table S2, ESI †) is intermediate between the Pd/TiO 2 and Cu/ TiO 2 catalysts (10.40 and 22.54 µmol g −1 , respectively, entries 2 and 3, Table S2, ESI †), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd-Cu alloy. 82,83 In addition to the redox sites, the acid sites of the catalysts play a crucial role in the CTH of furfural. 84,85 Therefore, in situ pyridine FT-IR analysis was carried out to elucidate the nature of the acid sites (Lewis and Brønsted) present in the catalysts.…”

Synergistic nanoalloy PdCu/TiO 2 catalyst for in situ hydrogenation of biomass-derived furfural at room temperature

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 μmol g −1 , entry 4, Table S2, ESI†) is intermediate between the Pd/TiO 2 and Cu/TiO 2 catalysts (10.40 and 22.54 μmol g −1 , respectively, entries 2 and 3, Table S2, ESI†), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd–Cu alloy. 82,83…”

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 µmol g −1 , entry 4, Table S2, ESI †) is intermediate between the Pd/TiO 2 and Cu/ TiO 2 catalysts (10.40 and 22.54 µmol g −1 , respectively, entries 2 and 3, Table S2, ESI †), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd-Cu alloy. 82,83 In addition to the redox sites, the acid sites of the catalysts play a crucial role in the CTH of furfural. 84,85 Therefore, in situ pyridine FT-IR analysis was carried out to elucidate the nature of the acid sites (Lewis and Brønsted) present in the catalysts.…”

Synthesizing Liquid Fuels Over Carbon‐Based Catalysts Via CO2 Conversion

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 , 113 , 114 ]…”

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79,81–103,105–114 ]…”

The lattice oxygen determines the methanol selectivity in CO 2 hydrogenation over ZnZrO x catalysts

“…When the reaction space velocity was increased, the contact time between the catalyst and the reaction gas decreased with a higher gas flow rate per unit volume of the catalyst. 38 A short contact time means that the catalytic reaction and by-product formation of the RWGS reaction is slowed down to some extent. The stability of CO 2 hydrogenation to methanol catalysts is critical as most catalysts are easily deactivated at higher…”

Synergistic nanoalloy PdCu/TiO 2 catalyst for in situ hydrogenation of biomass-derived furfural at room temperature

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 μmol g −1 , entry 4, Table S2, ESI†) is intermediate between the Pd/TiO 2 and Cu/TiO 2 catalysts (10.40 and 22.54 μmol g −1 , respectively, entries 2 and 3, Table S2, ESI†), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd–Cu alloy. 82,83…”

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 µmol g −1 , entry 4, Table S2, ESI †) is intermediate between the Pd/TiO 2 and Cu/ TiO 2 catalysts (10.40 and 22.54 µmol g −1 , respectively, entries 2 and 3, Table S2, ESI †), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd-Cu alloy. 82,83 In addition to the redox sites, the acid sites of the catalysts play a crucial role in the CTH of furfural. 84,85 Therefore, in situ pyridine FT-IR analysis was carried out to elucidate the nature of the acid sites (Lewis and Brønsted) present in the catalysts.…”

Synthesizing Liquid Fuels Over Carbon‐Based Catalysts Via CO2 Conversion

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 , 113 , 114 ]…”

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79,81–103,105–114 ]…”

The lattice oxygen determines the methanol selectivity in CO 2 hydrogenation over ZnZrO x catalysts

“…When the reaction space velocity was increased, the contact time between the catalyst and the reaction gas decreased with a higher gas flow rate per unit volume of the catalyst. 38 A short contact time means that the catalytic reaction and by-product formation of the RWGS reaction is slowed down to some extent. The stability of CO 2 hydrogenation to methanol catalysts is critical as most catalysts are easily deactivated at higher…”

Synergistic nanoalloy PdCu/TiO 2 catalyst for in situ hydrogenation of biomass-derived furfural at room temperature

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 μmol g −1 , entry 4, Table S2, ESI†) is intermediate between the Pd/TiO 2 and Cu/TiO 2 catalysts (10.40 and 22.54 μmol g −1 , respectively, entries 2 and 3, Table S2, ESI†), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd–Cu alloy. 82,83…”

“…80,81 The amount of H 2 uptake by PdCu species in the nanoalloyed catalyst (12.42 µmol g −1 , entry 4, Table S2, ESI †) is intermediate between the Pd/TiO 2 and Cu/ TiO 2 catalysts (10.40 and 22.54 µmol g −1 , respectively, entries 2 and 3, Table S2, ESI †), which is attributed to the presence of fewer PdO and CuO species due to the formation of Pd-Cu alloy. 82,83 In addition to the redox sites, the acid sites of the catalysts play a crucial role in the CTH of furfural. 84,85 Therefore, in situ pyridine FT-IR analysis was carried out to elucidate the nature of the acid sites (Lewis and Brønsted) present in the catalysts.…”

Synthesizing Liquid Fuels Over Carbon‐Based Catalysts Via CO2 Conversion

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79 , 81 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 , 101 , 102 , 103 , 105 , 106 , 107 , 108 , 109 , 110 , 111 , 112 , 113 , 114 ]…”

“…With sustainability at the forefront, detailing the role of carbon as identified in recent literature will be essential to propel the studies on carbon‐based catalysts in CO 2 conversion to liquid fuels. [ 79,81–103,105–114 ]…”

The lattice oxygen determines the methanol selectivity in CO 2 hydrogenation over ZnZrO x catalysts

“…When the reaction space velocity was increased, the contact time between the catalyst and the reaction gas decreased with a higher gas flow rate per unit volume of the catalyst. 38 A short contact time means that the catalytic reaction and by-product formation of the RWGS reaction is slowed down to some extent. The stability of CO 2 hydrogenation to methanol catalysts is critical as most catalysts are easily deactivated at higher…”