Cu‐Decorated ZnO Nanorod Array Integrated Structured Catalysts for Low‐Pressure CO₂ Hydrogenation to Methanol

Abstract

CO2 conversion into valuable chemicals and fuels, such as methanol, is one of the most practical routes for utilizing emitted CO2 and mitigating global warming. Herein, a 3D Cu‐decorated ZnO nanorod array based structured catalysts for efficient thermochemical CO2 hydrogenation to methanol at relatively low pressures (<10 atm) is successfully fabricated and demonstrated. This new type of nanorod array integrated structured catalysts has yielded a methanol formation rate of 1.9 mol h−1 kg−1 with a methanol selectivity of 56%, rivaling the state‐of‐the‐art powder‐form catalysts. The well‐dispersed copper species on the array structure as well as the array‐structure‐enhanced interfacial effect are key factors that improve the activity of the nanorod array catalysts in CO2 hydrogenation. The Cu‐ZnO nanorod array interface also suppresses reverse water‐gas shift reaction, reducing the selectivity to CO. Further improvement of the performance of the nanorod array based catalysts is demonstrated by tuning the ZnO nanorod array length. The developed nanorod array integrated monolithic catalysts also exhibit good stability during a long‐time continuous operation, demonstrating the potential and the feasibility of their practical implementation in industrial situation.

Advances in the Design of Heterogeneous Catalysts and Thermocatalytic Processes for CO2 Utilization

“…104 Based on this study, major focus has been given to Cu-based catalysts, mainly Cu-Zn combinations. [105][106][107][108][109]…”

“…In fact, more than 75% of catalysts studied in the last 10–15 years contain copper as an active metal phase. , In the 1960s, Imperial Chemical Industries developed a highly active ternary phase Cu–ZnO–Al 2 O 3 catalyst for the selective production of methanol from naphtha and natural gas under mild conditions . Based on this study, major focus has been given to Cu-based catalysts, mainly Cu–Zn combinations. − …”

Photo-assisted methanol synthesis via CO2 reduction under ambient pressure over plasmonic Cu/ZnO catalysts

“…Although methanol has been commercially produced from syngas (H2/CO) containing CO2 up to 30% of the total carbon over Cu-ZnO-Al2O3 catalysts at 200 -300 ºC under 5.0 -10.0 MPa, low methanol yields are obtained with pure CO2 as the carbon source [14][15][16]. Another technical hurdle is the low methanol yields under low pressure, which would impede the decentralized use of solar-or wind-generated H2 [17,18]. To enhance methanol yields under low pressure, various novel catalysts such as a Ni-Ga catalyst [19], Au nanoparticles activated on a CeOx/TiO2 interface [20] and a Ni-In-Al/SiO2 catalyst [21] were designed.…”

Ion-Exchange Loading Promoted Stability of Platinum Catalysts Supported on Layered Protonated Titanate-Derived Titania Nanoarrays

“…The dispersion and active surface area of Pt deposits were determined by H 2 pulse chemisorption carried out on a Micromeritics ChemiSorb 2720 unit connected with a Hiden HPR-20 R&D gas analysis system. 33 The prepared monolithic catalysts (0.5 g) were first oxidized in O 2 (20% in Ar) at 500 °C for 60 min and then reduced in H 2 (4% in Ar) at 300 °C for 60 min. The samples were further flushed by Ar at 300 °C for 30 min and then cooled down to room temperature in Ar.…”