The Ni5Ga3 alloy supported on ZrO2 is a promising catalyst for the reduction of CO2 due to its higher selectivity to methanol at ambient pressure, e.g., activity comparable to industrial catalysts. However, our atomistic understanding of the role of the cooperative effects induced by the Ni5Ga3 alloy formation and its Ni5Ga3/ZrO2 interface in the CO2 reduction is still far from satisfactory. In this work, we tackle these questions by employing density functional theory calculations to investigate the adsorption properties of key CO2 reduction intermediates (CO2, H2, cis-COOH, trans-COOH, HCOO, CO, HCO, and COH) on Ni8, Ga8, Ni5Ga3, (ZrO2)16, and Ni5Ga3/(ZrO2)16. We found that Ni containing clusters tended to assume wetting configurations on the (ZrO2)16 cluster, while the presence of Ga atoms weakens the adsorption energies on the oxide surface. We also observed that CO2 was better activated on the metal–oxide interfaces and on the oxide surface, where it was able to form CO3-like structures. Meanwhile, H2 activation was only observed on Ni sites, which indicates the importance of distinct adsorption sites that can favor different CO2 reduction steps. Moreover, the formation of the metal–oxide interface showed to be beneficial for the adsorption of COOH isomers and unfavorable for the adsorption of HCOO.
REFERENCES
1.
Q.
Tang
, W.
Ji
, C. K.
Russell
, Z.
Cheng
, Y.
Zhang
, M.
Fan
, and Z.
Shen
, “Understanding the catalytic mechanisms of CO2 hydrogenation to methanol on unsupported and supported Ga-Ni clusters
,” Appl. Energy
253
, 113623
(2019
).2.
S.
Solomon
, G.-K.
Plattner
, R.
Knutti
, and P.
Friedlingstein
, “Irreversible climate change due to carbon dioxide emissions
,” Proc. Natl. Acad. Sci. U. S. A.
106
, 1704
–1709
(2009
).3.
United in Science 2021,
World Meteorological Organization
, Genebra, Switzerland
, 2021
.4.
A.
Álvarez
, A.
Bansode
, A.
Urakawa
, A. V.
Bavykina
, T. A.
Wezendonk
, M.
Makkee
, J.
Gascon
, and F.
Kapteijn
, “Challenges in the greener production of formates/formic acid, methanol, and DME by heterogeneously catalyzed CO2 hydrogenation processes
,” Chem. Rev.
117
, 9804
–9838
(2017
).5.
H.
Yang
, C.
Zhang
, P.
Gao
, H.
Wang
, X.
Li
, L.
Zhong
, W.
Wei
, and Y.
Sun
, “A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons
,” Catal. Sci. Technol.
7
, 4580
–4598
(2017
).6.
W.-C.
Liu
, J.
Baek
, and G. A.
Somorjai
, “The methanol economy: Methane and carbon dioxide conversion
,” Top. Catal.
61
, 530
–541
(2018
).7.
X.
Jiang
, X.
Nie
, X.
Guo
, C.
Song
, and J. G.
Chen
, “Recent advances in carbon dioxide hydrogenation to methanol via heterogeneous catalysis
,” Chem. Rev.
120
, 7984
–8034
(2020
).8.
Y.
Li
, S. H.
Chan
, and Q.
Sun
, “Heterogeneous catalytic conversion of CO2: A comprehensive theoretical review
,” Nanoscale
7
, 8663
–8683
(2015
).9.
J.
Zhong
, X.
Yang
, Z.
Wu
, B.
Liang
, Y.
Huang
, and T.
Zhang
, “State of the art and perspectives in heterogeneous catalysis of CO2 hydrogenation to methanol
,” Chem. Soc. Rev.
49
, 1385
(2020
).10.
W.
Wang
, S.
Wang
, X.
Ma
, and J.
Gong
, “Recent advances in catalytic hydrogenation of carbon dioxide
,” Chem. Soc. Rev.
40
, 3703
–3727
(2011
).11.
F.
Studt
, I.
Sharafutdinov
, F.
Abild-Pedersen
, C. F.
Elkjær
, J. S.
Hummelshøj
, S.
Dahl
, I.
Chorkendorff
, and J. K.
Nørskov
, “Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
,” Nat. Chem.
6
, 320
–324
(2014
).12.
I.
Sharafutdinov
, C. F.
Elkjær
, H. W.
Pereira de Carvalho
, D.
Gardini
, G. L.
Chiarello
, C. D.
Damsgaard
, J. B.
Wagner
, J.-D.
Grunwaldt
, S.
Dahl
, and I.
Chorkendorff
, “Intermetallic compounds of Ni and Ga as catalysts for the synthesis of methanol
,” J. Catal.
320
, 77
–88
(2014
).13.
Q.
Tang
, Z.
Shen
, L.
Huang
, T.
He
, H.
Adidharma
, A. G.
Russell
, and M.
Fan
, “Synthesis of methanol from CO2 hydrogenation promoted by dissociative adsorption of hydrogen on a Ga3Ni5(221) surface
,” ChemPhysChem
19
, 18539
–18555
(2017
).14.
P.
Chen
, G.
Zhao
, Y.
Liu
, and Y.
Lu
, “Monolithic Ni5Ga3/SiO2/Al2O3/Al-fiber catalyst for CO2 hydrogenation to methanol at ambient pressure
,” Appl. Catal., A
562
, 234
–240
(2018
).15.
C. L.
Chiang
, K. S.
Lin
, and Y. G.
Lin
, “Preparation and characterization of Ni5Ga3 for methanol formation via CO2 hydrogenation
,” Top. Catal.
60
, 685
–696
(2017
).16.
K.
Ahmad
and S.
Upadhyayula
, “Selective conversion of CO2 to methanol over intermetallic Ga-Ni catalyst: Microkinetic modeling
,” Fuel
278
, 118296
(2020
).17.
A.
Gallo
, J. L.
Snider
, D.
Sokaras
, D.
Nordlund
, T.
Kroll
, H.
Ogasawara
, L.
Kovarik
, M. S.
Duyar
, and T. F.
Jaramillo
, “Ni5Ga3 catalysts for CO2 reduction to methanol: Exploring the role of Ga surface oxidation/reduction on catalytic activity
,” Appl. Catal., B
267
, 118369
(2020
).18.
L. F.
Rasteiro
, M. A.
Rossi
, J. M.
Assaf
, and E. M.
Assaf
, “Low-pressure hydrogenation of CO2 to methanol over Ni-Ga alloys synthesized by a surfactant-assisted co-precipitation method and a proposed mechanism by DRIFTS analysis
,” Catal. Today
381
, 261
–271
(2020
).19.
K.
Ahmad
and S.
Upadhyayula
, “Kinetics of CO2 hydrogenation to methanol over silica supported intermetallic Ga3Ni5 catalyst in a continuous differential fixed bed reactor
,” Int. J. Hydrogen Energy
45
, 1140
–1150
(2020
).20.
Q.
Tang
, Z.
Shen
, C. K.
Russell
, and M.
Fan
, “Thermodynamic and kinetic study on carbon dioxide hydrogenation to methanol over a Ga3Ni5(111) surface: The effects of step edge
,” J. Phys. Chem. C
122
, 315
–330
(2018
).21.
Y.
Lou
, M.
Steib
, Q.
Zhang
, K.
Tiefenbacher
, A.
Horváth
, A.
Jentys
, Y.
Liu
, and J. A.
Lercher
, “Design of stable Ni/ZrO2 catalysts for dry reforming of methane
,” J. Catal.
356
, 147
–156
(2017
).22.
K.
Li
and J. G.
Chen
, “CO2 hydrogenation to methanol over ZrO2-containing catalysts: Insights into ZrO2 induced synergy
,” ACS Catal.
9
, 7840
–7861
(2019
).23.
T.
Witoon
, J.
Chalorngtham
, P.
Dumrongbunditkul
, M.
Chareonpanich
, and J.
Limtrakul
, “CO2 hydrogenation to methanol over Cu/ZrO2 catalysts: Effects of zirconia phases
,” Chem. Eng. J.
293
, 327
–336
(2016
).24.
F.
Arena
, G.
Italiano
, K.
Barbera
, S.
Bordiga
, G.
Bonura
, L.
Spadaro
, and F.
Frusteri
, “Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH
,” Appl. Catal., A
350
, 16
–23
(2008
).25.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, “Generalized gradient approximation made simple
,” Phys. Rev. Lett.
77
, 3865
–3868
(1996
).26.
A.
Tkatchenko
and M.
Scheffler
, “Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data
,” Phys. Rev. Lett.
102
, 073005
(2009
).27.
A.
Tkatchenko
, R. A.
DiStasio
, R.
Car
, and M.
Scheffler
, “Accurate and efficient method for many-body van der Waals interactions
,” Phys. Rev. Lett.
108
, 236402
(2012
).28.
K. F.
Andriani
, J.
Mucelini
, and J. L. F.
Da Silva
, “Methane dehydrogenation on 3d 13-atom transition-metal clusters: A density functional theory investigation combined with Spearman rank correlation analysis
,” Fuel
275
, 117790
(2020
).29.
P.
Felício-Sousa
, K. F.
Andriani
, and J. L. F.
Da Silva
, “Ab initio investigation of the role of the d-states occupation on the adsorption properties of H2, CO, CH4 and CH3OH on the Fe13, Co13, Ni13 and Cu13 clusters
,” Phys. Chem. Chem. Phys.
23
, 8739
–8751
(2021
).30.
E.
van Lenthe
, J. G.
Snijders
, and E. J.
Baerends
, “The zero-order regular approximation for relativistic effects: The effect of spin–orbit coupling in closed shell molecules
,” J. Chem. Phys.
105
, 6505
–6516
(1996
).31.
V.
Blum
, R.
Gehrke
, F.
Hanke
, P.
Havu
, V.
Havu
, X.
Ren
, K.
Reuter
, and M.
Scheffler
, “Ab initio molecular simulations with numeric atom-centered orbitals
,” Comput. Phys. Commun.
180
, 2175
–2196
(2009
).32.
V.
Havu
, V.
Blum
, P.
Havu
, and M.
Scheffler
, “Efficient integration for all-electron electronic structure calculation using numeric basis functions
,” J. Comput. Phys.
228
, 8367
–8379
(2009
).33.
34.
L. F.
Rasteiro
, R. A.
De Sousa
, L. H.
Vieira
, V. K.
Ocampo-Restrepo
, L. G.
Verga
, J. M.
Assaf
, J. L.
Da Silva
, and E. M.
Assaf
, “Insights into the alloy-support synergistic effects for the CO2 hydrogenation towards methanol on oxide-supported Ni5Ga3 catalysts: An experimental and DFT study
,” Appl. Catal., B
302
, 120842
(2021
).35.
Y.
Yang
, M. G.
White
, and P.
Liu
, “Theoretical study of methanol synthesis from CO2 hydrogenation on metal-doped Cu(111) surfaces
,” J. Phys. Chem. C
116
, 248
–256
(2012
).36.
A. S.
Chaves
, M. J.
Piotrowski
, and J. L. F.
Da Silva
, “Evolution of the structural, energetic, and electronic properties of the 3d, 4d, and 5d transition-metal clusters (30 TMn systems for n = 2–15): A density functional theory investigation
,” Phys. Chem. Chem. Phys.
19
, 15484
–15502
(2017
).37.
F.
Orlando Morais
, K. F.
Andriani
, and J. L. F.
Da Silva
, “Investigation of the stability mechanisms of eight-atom binary metal clusters using DFT calculations and k-means clustering algorithm
,” J. Chem. Inf. Model.
61
, 3411
–3420
(2021
).38.
M.
Rupp
, A.
Tkatchenko
, K. R.
Müller
, and O. A.
Von Lilienfeld
, “Fast and accurate modeling of molecular atomization energies with machine learning
,” Phys. Rev. Lett.
108
, 058301
(2012
).39.
S.
Lloyd
, “Least squares quantization in PCM
,” IEEE Trans. Inf. Theory
28
, 129
–137
(1982
).40.
A. R.
Puigdollers
, F.
Illas
, and G.
Pacchioni
, “Structure and properties of zirconia nanoparticles from density functional theory calculations
,” J. Phys. Chem. C
120
, 4392
–4402
(2016
).41.
A.
Ruiz Puigdollers
, S.
Tosoni
, and G.
Pacchioni
, “Turning a nonreducible into a reducible oxide via nanostructuring: Opposite behavior of bulk ZrO2 and ZrO2 nanoparticles toward H2 adsorption
,” J. Phys. Chem. C
120
, 15329
–15337
(2016
).42.
E.
Albanese
, A.
Ruiz Puigdollers
, and G.
Pacchioni
, “Theory of ferromagnetism in reduced ZrO2−x nanoparticles
,” ACS Omega
3
, 5301
–5307
(2018
).43.
L.
Zibordi-Besse
, L. G.
Verga
, V. K.
Ocampo-Restrepo
, and J. L. F.
Da Silva
, “Ab initio investigation of the formation mechanism of nano-interfaces between 3d-late transition-metals and ZrO2 nanoclusters
,” Phys. Chem. Chem. Phys.
22
, 8067
–8076
(2020
).44.
S.-H.
Cha
, “Comprehensive survey on distance/similarity measures between probability density functions
,” Int. J. Math. Models Methods Appl. Sci.
1
, 300
–307
(2007
).45.
R.
Gehrke
and K.
Reuter
, “Assessing the efficiency of first-principles basin-hopping sampling
,” Phys. Rev. B
79
, 085412
(2009
).46.
M. D.
Hanwell
, D. E.
Curtis
, D. C.
Lonie
, T.
Vandermeersch
, E.
Zurek
, and G. R.
Hutchison
, “Avogadro: An advanced semantic chemical editor, visualization, and analysis platform
,” J. Cheminf.
4
, 17
(2012
).47.
G.
Herzberg
, Molecular Spectra and Molecular Structure. Vol. 3: Electronic Spectra and Electronic Structure of Polyatomic Molecules
(D. Van Nostrand Company
, 1966
).48.
S.
Demir
and M. F.
Fellah
, “A DFT study on Pt doped (4,0) SWCNT: CO adsorption and sensing
,” Appl. Surf. Sci.
504
, 144141
(2020
).49.
M.
Kamel
, H.
Raissi
, A.
Morsali
, and K.
Mohammadifard
, “Density functional theory study towards investigating the adsorption properties of the γ-Fe2O3 nanoparticles as a nanocarrier for delivery of Flutamide anticancer drug
,” Adsorption
26
, 925
–939
(2020
).50.
J. L. F.
Da Silva
, “Effective coordination concept applied for phase change compounds
,” J. Appl. Phys.
109
, 023502
(2011
).51.
V. K.
Ocampo-Restrepo
, L.
Zibordi-Besse
, and J. L. F.
Da Silva
, “Ab initio investigation of the atomistic descriptors in the activation of small molecules on 3d transition-metal 13-atom clusters: The example of H2, CO, H2O and CO2
,” J. Chem. Phys.
151
, 214301
(2019
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
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