Understanding the structure-performance relationship of cubic In2O3 catalysts for CO2 hydrogenation

https://doi.org/10.1016/j.jcou.2021.101543Get rights and content

Highlights

  • The rate-determining step of CH3OH formation from CO2 hydrogenation is found to be site-dependent.

  • The catalytic property for each Ov site on cubic In2O3 surfaces is predicted to establish the structure-performance relationship.

  • Tri-coordinated Ov sites favor CH3OH formation, whereas bi-coordinated Ov sites favor CO formation.

Abstract

Reaction mechanism and catalytic activities of methanol (CH3OH) and CO formations from CO2 hydrogenation at all the different surface oxygen vacancy (Ov) sites on the stable cubic In2O3 (c-In2O3) (111) flat surface and (110) flat and (110) step surfaces were thoroughly investigated in order to establish the structure-performance relationship using density functional theory calculations. For CH3OH formation, the R2 step for bidentate formate intermediate (bi-HCOO*) hydrogenation to the dioxymethylene intermediate (H2COO*), or the R3 step for H2COO* dissociation to the formaldehyde intermediate (CH2O*) and surface O atom, was calculated to be the rate-determining step (RDS), whereas for CO formation, the R1a step for bent CO2 adsorbate (bt-CO2*) protonation to the carboxylate intermediate (COOH*), was calculated to be the only RDS. Further data science analysis using the perceptron learning and decision tree algorithms shows that the RDS for CH3OH formation for a given Ov site can be determined by the stability of two key reaction intermediates (H2COO* and CH2O*) along with the formation energy of the Ov site. Linear regression analysis was also performed to establish linear relationships between the activation barriers and corresponding reaction energies for R2 and R3 steps, which can also be useful in determining the actual RDS for CH3OH formation. Although the adsorption energies of the linear CO2 configuration intermediate (ln-CO2*) and the bt-CO2* as well as the difference between the activation barriers of the RDS for CO and CH3OH formations are required for reliably predicting the catalytic activity and product selectivity, our studies suggest a simple and intuitive structure-performance relationship for the c-In2O3 catalyst that tri-coordinated Ov sites favor CH3OH formation, whereas bi-coordinated Ov sites favor CO formation.

Introduction

Methanol (CH3OH) synthesis form CO2 hydrogenation has attracted increasing attention for its importance in the CO2 utilization strategy in recent decades. Nobel Laureate George Olah once proposed the “methanol economy” [1], according to which the conversion of CO2 to CH3OH using hydrogen from renewable energy resources may eventually relieve our heavy reliance on fossil fuels. CH3OH synthesis form CO2 hydrogenation involves two key reactions. The main reaction is CH3OH formation from CO2 (CO2 + 3H2 → CH3OH + H2O), which is exothermic (ΔrHɵ: −49.50 kJ mol−1) at the room temperature [2]. The competing side reaction is the reverse water-gas shift (RWGS) reaction (CO2 + H2 → CO + H2O), which is endothermic (ΔrHɵ: +41.20 kJ mol−1) at the room temperature [2,3]. Thus, thermodynamic consideration suggests that the low temperature makes CH3OH formation via CO2 hydrogenation possible.

Cu- and Pd-based catalysts were widely studied for CH3OH synthesis form CO2 hydrogenation, based on a recent analysis of the literature [4]. Under industrially relevant reaction conditions (T = 493−573 K, P = 50−100 bar), the Cu-ZnO-Al2O3 catalyst is used to convert CO2-containing syngas (CO/CO2/H2) to CH3OH. Behrens et al. [5] identified the crucial atomic level structure motif for the Cu-ZnO-Al2O3 catalyst by combined experiments and density functional theory (DFT) calculations, and Cu steps decorated with Zn atoms were identified as the active sites, which were stabilized by surface species and bulk defects. Kattel et al. [6] investigated the active sites of the Cu-ZnO catalyst for CH3OH synthesis form CO2 hydrogenation by combining experimental characterizations, DFT calculations as well as kinetic Monte Carlo simulations. They compared the catalytic activities of the Zn/Cu bimetallic and ZnO/Cu oxide-on-metal model catalysts, and found that the surface Zn on the Zn/Cu catalyst can be transformed to ZnO, and the Zn/Cu reached the same level of catalytic activity as the ZnO/Cu with the same Zn coverage. Thus, their studies suggest the crucial role of the synergy between Cu and ZnO at the interface in this reaction. Although the Cu-ZnO-Al2O3 catalyst is widely adopted for the industrial production of CH3OH from CO2-containing syngas, they have several disadvantages when directly applied to CH3OH synthesis from CO2 hydrogenation. Firstly, water formed during the reaction severely hinders the CO2 hydrogenation reaction at the active site, as it induces sintering of the active phase, and easily deactivates the catalyst [7]. Secondly, in the industrially relevant temperature range of 493−573 K, a large amount of undesired CO is produced as the byproduct from the RWGS reaction on this catalyst, which greatly limits the CH3OH selectivity [8]. Thus, superior water-resistant and RWGS-suppressing catalysts are needed for this reaction.

In recent years, higher CH3OH selectivity in the CO2 hydrogenation reaction was achieved by using indium oxide (In2O3) based catalysts. Two research groups [9,10] investigated the reaction mechanism of CH3OH synthesis from CO2 hydrogenation on the pure In2O3 surface using DFT calculations and reached an agreement that the reaction mechanism of CH3OH formation on the defective In2O3 surface occurred via the formate (HCOO) route, where CO2 was stepwise hydrogenated into the formate intermediate (HCOO*), dioxymethylene intermediate (H2COO*), formaldehyde intermediate (CH2O*), methoxy intermediate (CH3O*), and CH3OH. Martin et al. [11] showed experimentally that the In2O3 catalyst could indeed be used for CO2 hydrogenation to methanol, and methanol selectivity reaches 100 % using the In2O3/ZrO2 mixed-oxide catalyst, which has a remarkable stability under industrially relevant conditions (T = 473−573 K, P = 1−5 MPa, GHSV = 16000−48,000 cm3 h−1gcat-1 and H2/CO2/Ar = 4/1/1.5). Further experimental studies of Sun et al. [12] showed that CO2 conversion increases at increasing temperature and pressure, although the formation rate and selectivity of CH3OH first increase with the temperature, and then reach the maximum at 603 K and decrease thereafter. At T =603 K, P =4 MPa, GHSV = 15,000 cm3 h−1gcat−1 and H2/CO2/N2 = 3/1/1, CO2 conversion and CH3OH selectivity reach 7.13 % and 39.7 %, respectively, over the In2O3 catalyst.

Previously, our research group developed bifunctional catalysts composed of In2O3 (or In2O3/ZrO2 composite oxide) and zeolite (H-form Zeolite Socony Mobile-5 and SAPO-34) for gasoline (C5°-C11°) synthesis and lower olefins (C2=-C4=) synthesis directly from CO2 hydrogenation [13,14]. We showed that the CO2 hydrogenation reaction on the In2O3/ZrO2 composite oxide can proceed at the relatively high reaction temperature of ∼673 K, and doping Zr into In2O3 helps to stabilize the key adsorbates at the Ov site near the Zr dopant [14]. For CH3OH synthesis form CO2 hydrogenation, compared with the In2O3/ZrO2 mixed-oxide catalyst, the pure In2O3 catalyst results in lower CO2 conversion rate as well as inferior CH3OH selectivity at higher reaction temperature. Recent experimental and computational studies further suggest that the product selectivity strongly depends on the crystal phase and surface morphology for CO2 hydrogenation [15,16]. However, due to the presence of multiple distinct Ov sites on the different surface terminations, the precise relationship between the structure of the In2O3 catalyst and its catalytic performance in the CO2 hydrogenation reaction remains to be firmly established, which is vital for the development of more efficient oxide catalysts for this reaction.

In this work, the reaction mechanism and catalytic activities of all the different surface oxygen vacancy (Ov) sites on the stable cubic In2O3 (c-In2O3) surfaces for CH3OH and CO formation from CO2 hydrogenation were thoroughly investigated in order to establish the structure-performance relationship by performing data science analysis using several simple and interpretable classification algorithms. The (111) flat and (110) flat ((111)-f and (110)-f) surfaces, as well as the (110) step ((110)-s) surface of c-In2O3 were considered, which are the most stable surfaces of the most stable phase of In2O3, as shown by recent experiments [17,18], DFT calculations [[19], [20], [21]] and detailed structural characterization of the c-In2O3 catalysts in our recent work [16]. This study shows that data science tools are very useful for learning from a large amount of computational data and can significantly improve our understanding of the structure-performance relationship of complex heterogeneous catalysts.

Section snippets

Computational methods

We performed periodic DFT calculations using the Vienna ab initio simulation package (VASP) [22,23] with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional [24] and the projector-augmented wave (PAW) potentials, which account for the valence-core electron interactions [25]. The detailed calculation parameters on this system in this work were identical to those in our previous works. [13,14,16,26,27].

The optimized primitive unit cell based on our previous work [13] was used to

Selection of surface oxygen vacancies

The 12 surface Ov sites from Ov1 to Ov12 on the perfect (111)-f surface (Figure S1b) are classified into four types from high to low Ef,Ov: (1) Ov7, Ov9, Ov11, (2) Ov4, Ov10, Ov12, (3) Ov2, Ov5, Ov6, and (4) Ov1, Ov3, Ov8, according to our previous work [26]. In our initial calculations of the reaction mechanism, we chose the most types of Ov sites with the highest and the lowest Ov formation energies. Thus, the Ov7 site (Figure S1c) with the highest formation energy and the Ov3 site with the

Conclusions

Reaction mechanism and catalytic activities for CH3OH and CO formations from CO2 hydrogenation at all the different surface Ov sites on the stable (111)-flat surface and (110)-f and (110)-s surfaces were thoroughly investigated in order to establish the structure-performance relationship by combining DFT calculations and data science analysis. Both bi−HCOO* hydrogenation to the H2COO* (R2) and H2COO* dissociation to the CH2O* with surface O atom (R3) can be the actual RDS for CH3OH formation,

CRediT authorship contribution statement

Bin Qin: Conceptualization, Formal analysis, Investigation, Visualization, Writing - original draft, Writing - review & editing. Zhimin Zhou: Software, Formal analysis. Shenggang Li: Conceptualization, Resources, Writing - original draft, Writing - review & editing, Supervision, Project administration, Funding acquisition. Peng Gao: Project administration, Funding acquisition.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work was supported by Shell Global Solutions B.V. (CW373032); Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21090204); and Youth Innovation Promotion Association CAS (2018330).

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