Dynamic Structure and Subsurface Oxygen Formation of a Working Copper Catalyst under Methanol Steam Reforming Conditions: An in Situ Time-Resolved Spectroscopic Study

In this work, the electronic properties of the metal sites in cubic and monoclinic ZrO2 supported Pd and PdCu catalysts have been investigated using CO as probe molecule in in-situ IR studies, and the surface composition of the outermost layers has been studied by APXPS (Ambient Pressure X-ray Photoemission Spectroscopy). The reaction products were followed by mass spectrometry, making it possible to relate the chemical properties of the catalysts under reaction conditions with their selectivity. Combining these techniques, it has been shown that the structure of the support (monoclinic or cubic ZrO2) affects the metal dispersion, mobility, and reorganization of metal sites under methanol steam reforming (MSR) conditions, influencing the oxidation state of surface metal species, with important consequences in the catalytic activity. Correlating the mass spectra of the reaction products with these spectroscopic studies, it was possible to conclude that electropositive metal species play an imperative role for high CO2 and H2 selectivity in the MSR reaction (less CO formation).

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Development of durable copper catalyst for hydrogen production by high temperature methanol steam reforming

International Journal of Hydrogen Energy ◽

10.1016/j.ijhydene.2013.08.066 ◽

2013 ◽

Vol 38 (32) ◽

pp. 13950-13960 ◽

Cited By ~ 12

Author(s):

Yasuyuki Matsumura

Keyword(s):

High Temperature ◽

Hydrogen Production ◽

Steam Reforming ◽

Copper Catalyst ◽

Methanol Steam Reforming

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In Situ Reduction of a CuO/ZnO/CeO2/ZrO2 Catalyst Washcoat Supported on Al2O3 Foam Ceramic by Glycerol for Methanol Steam Reforming in a Microreactor

Industrial & Engineering Chemistry Research ◽

10.1021/acs.iecr.1c01180 ◽

2021 ◽

Author(s):

Moyu Liao ◽

Hang Qin ◽

Wenming Guo ◽

Pengzhao Gao ◽

Hanning Xiao

Keyword(s):

Steam Reforming ◽

Methanol Steam Reforming ◽

In Situ Reduction ◽

Foam Ceramic ◽

Zro2 Catalyst

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The Promoting Effect of Ni on Glycerol Hydrogenolysis to 1,2-Propanediol with In Situ Hydrogen from Methanol Steam Reforming Using a Cu/ZnO/Al2O3 Catalyst

Catalysts ◽

10.3390/catal9050412 ◽

2019 ◽

Vol 9 (5) ◽

pp. 412 ◽

Cited By ~ 7

Author(s):

Yuanqing Liu ◽

Xiaoming Guo ◽

Garry Rempel ◽

Flora Ng

Keyword(s):

Steam Reforming ◽

Molecular Hydrogen ◽

Biodiesel Production ◽

Precipitation Method ◽

Methanol Steam Reforming ◽

Phase Reaction ◽

Promoting Effect ◽

High Hydrogen ◽

Al2o3 Catalyst

Production of green chemicals using a biomass derived feedstock is of current interest. Among the processes, the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PD) using externally supplied molecular hydrogen has been studied quite extensively. The utilization of methanol present in crude glycerol from biodiesel production can avoid the additional cost for molecular hydrogen storage and transportation, as well as reduce the safety risks due to the high hydrogen pressure operation. Recently the hydrogenolysis of glycerol with a Cu/ZnO/Al2O3 catalyst using in situ hydrogen generated from methanol steam reforming in a liquid phase reaction has been reported. This paper focusses on the effect of added Ni on the activity of a Cu/ZnO/Al2O3 catalyst prepared by an oxalate gel-co-precipitation method for the hydrogenolysis of glycerol using methanol as a hydrogen source. It is found that Ni reduces the conversion of glycerol but improves the selectivity to 1,2-PD, while a higher conversion of methanol is observed. The promoting effect of Ni on the selectivity to 1,2-PD is attributed to the slower dehydration of glycerol to acetol coupled with a higher availability of in situ hydrogen produced from methanol steam reforming and the higher hydrogenation activity of Ni towards the intermediate acetol to produce 1,2-PD.

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