Machine learning-guided discovery of γ-Al2O3 as defect-rich structural ensemble governs single-atom Pt catalysis

Ka Lok Cliff Choong; Ran Luo; Zhi-Jian Zhao; Jinlong Gong

doi:10.1007/s11705-026-2690-2

ENG. Chem. Eng. ›› 2026, Vol. 20 ›› Issue (10) :77 DOI: 10.1007/s11705-026-2690-2

RESEARCH ARTICLE

Machine learning-guided discovery of

γ

-Al₂O₃as defect-rich structural ensemble governs single-atom Pt catalysis

Ka Lok Cliff Choong ¹^,^‡
, Ran Luo ³^,^‡
, Zhi-Jian Zhao ¹^,²
, Jinlong Gong ¹^,²^,⁴^,⁵

Author information +

History +

PDF (3342KB)

Abstract

$γ$ -Al₂O₃ is one of the most widely used catalyst supports in heterogeneous catalysis, yet its catalytic role remains unclear due to intrinsic structural disorder and complex surface species. This paper describes the development of a high-accuracy Al–O–H machine learning interatomic potential combined with global optimization to explore the structural landscape of $γ$ -Al₂O₃ and its influence on propane dehydrogenation over single-atom Pt catalysts. Two energetically favorable structures, $γ$ -no aluminum vacancy (NAV) and $γ$ -aluminum vacancy (AV), are identified with energies lower than the conventional model by up to 34.44 meV∙(f.u.)^–1. These optimized structures expose abundant penta-coordinated Al³⁺ sites on the (100) surface, serving as preferred anchoring sites for Pt atoms. Simulated X-ray diffraction patterns indicate that $γ$ -AV shows better qualitative agreement with experimental data. Surface phase diagrams further reveal that defect-rich surfaces are thermodynamically stabilized under realistic reaction conditions. Catalytic calculations demonstrate that $γ$ -NAV and $γ$ -AV significantly reduce propane dehydrogenation activation barriers through enhanced metal-support interactions associated with penta-coordinated Al³⁺ sites and defect-modulated local environments. These results suggest that $γ$ -Al₂O₃ is better described as an ensemble of defect-rich surface configurations rather than a single crystal structure. These findings establish a direct relationship between atomic structure, defect chemistry, and catalytic performance in $γ$ -Al₂O₃.

Graphical abstract

Keywords

γ-Al₂O₃ / machine learning interatomic potential / propane dehydrogenation / single-atom catalysis / defect chemistry

Cite this article

Download citation ▾

Ka Lok Cliff Choong, Ran Luo, Zhi-Jian Zhao, Jinlong Gong. Machine learning-guided discovery of

γ

-Al₂O₃as defect-rich structural ensemble governs single-atom Pt catalysis. ENG. Chem. Eng., 2026, 20 (10) : 77 DOI:10.1007/s11705-026-2690-2

登录浏览全文

4963

注册一个新账户忘记密码

References

Publishing order | Descend order by publishing year | Descend order by cited within

[1]	Busca G . The surface of transitional aluminas: a critical review. Catalysis Today, 2014, 226: 2–13

[2]	Trueba M , Trasatti S P . γ-Alumina as a support for catalysts: a review of fundamental aspects. European Journal of Inorganic Chemistry, 2005, 2005(17): 3393–3403

[3]	Levin I , Brandon D . Metastable alumina polymorphs: crystal structures and transition sequences. Journal of the American Ceramic Society, 1998, 81(8): 1995–2012

[4]	Chen Z , Wu F , Gao X Q , He L , Lu A H . Study on preparation of spherical Al₂O₃ by nucleation-coating method and its application in propane dehydrogenation. Low-Carbon Chemistry and Chemical Engineering, 2024, 49(2): 49–59

[5]	Frontera P , Macario A , Ferraro M , Antonucci P . Supported catalysts for CO₂ methanation: a review. Catalysts, 2017, 7(2): 59

[6]

Gao S T , Li X B , Wang Y L , Shen L T , Peng Z H , Liu G H , Zhou Q S , Guo J , Qi T G . Preparation of propane dehydrogenation catalyst spherical alumina support from pseudo boehmite: structural and performance comparison with commercial spherical alumina support. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2025, 726: 137864

[7]	Yu Y , Zhang Y , Zhang Y , Wu Q , Shi D , Chen K , Li H . Research progress of bulk metal oxides in non-oxidative propane dehydrogenation. Applied Chemical Industry, 2023, 49(6): 789–805

[8]	Li S Y , Li Q , Yang H H , Wang S , Dong M , Wang J G , Fan W B . Catalyst development and design in propane dehydrogenation. Chemical Research in Chinese Universities, 2026, 42(1): 43–62

[9]	Liu S J , He K , Bi Y F , Song L J . A review of the morphological regulation of γ-Al₂O₃ support and its effect on propane dehydrogenation catalysts. Journal of Petrochemical Universities, 2024, 37(2): 31–41

[10]	Liu Q Y , He C . Research progress on Pt-based catalysts for propane dehydrogenation reaction. Energy Environmental Protection, 2024, 38(4): 53–66

[11]	Wang G W , Zhou L H , Zhang H L , Zhu C L , Zhu X L , Shan H H . The stabilization effect of Al₂O₃ on unconventional Pb/SiO₂ catalyst for propane dehydrogenation. Frontiers of Chemical Science and Engineering, 2023, 17(10): 1423–1429

[12]	Sun M L , Hu Z P , Wang H Y , Suo Y J , Yuan Z Y . Design strategies of stable catalysts for propane dehydrogenation to propylene. ACS Catalysis, 2023, 13(7): 4719–4741

[13]	Busca G . Catalytic materials based on silica and alumina: structural features and generation of surface acidity. Progress in Materials Science, 2019, 104: 215–249

[14]	Knözinger H , Ratnasamy P . Catalytic aluminas: surface models and characterization of surface sites. Catalysis Reviews, 1978, 17(1): 31–70

[15]	Shan Y O , Hu H M , Fan X Q , Zhao Z . Recent progress in catalytic dehydrogenation of propane over Pt-based catalysts. Physical Chemistry Chemical Physics, 2023, 25(28): 18609–18622

[16]	Yu Q Q , Yu T , Chen H Y , Fang G Z , Pan X L , Bao X H . The effect of Al³⁺ coordination structure on the propane dehydrogenation activity of Pt/Ga/Al₂O₃ catalysts. Journal of Energy Chemistry, 2020, 41: 93–99

[17]	Prins R . On the structure of γ-Al₂O₃. Journal of Catalysis, 2020, 392: 336–346

[18]	Paglia G , Buckley C E , Rohl A L , Hunter B A , Hart R D , Hanna J V , Byrne L T . Tetragonal structure model for boehmite-derived γ-alumina. Physical Review B, 2003, 68(14): 144110

[19]	Krokidis X , Raybaud P , Gobichon A E , Rebours B , Euzen P , Toulhoat H . Theoretical study of the dehydration process of boehmite to γ-alumina. The Journal of Physical Chemistry B, 2001, 105(22): 5121–5130

[20]	Digne M , Sautet P , Raybaud P , Euzen P , Toulhoat H . Use of DFT to achieve a rational understanding of acid-basic properties of γ-alumina surfaces. Journal of Catalysis, 2004, 226(1): 54–68

[21]	Wolverton C , Hass K C . Phase stability and structure of spinel-based transition aluminas. Physical Review B, 2000, 63(2): 024102

[22]	Ferreira A R , Martins M J F , Konstantinova E , Capaz R B , Souza W F , Chiaro S S X , Leitão A A . Direct comparison between two γ-alumina structural models by DFT calculations. Journal of Solid State Chemistry, 2011, 184(5): 1105–1111

[23]	Sun M Y , Nelson A E , Adjaye J . Examination of spinel and nonspinel structural models for γ-Al₂O₃ by DFT and rietveld refinement simulations. The Journal of Physical Chemistry B, 2006, 110(5): 2310–2317

[24]	Yang X , Shang C , Liu Z P . Resolving the atomic structure of γ-alumina: a non-spinel phase with a distorted anion lattice and three adjacent long channels. Journal of Materials Chemistry A, 2025, 13(23): 17429–17433

[25]	Kwak J H , Hu J Z , Mei D H , Yi C W , Kim D H , Peden C H F , Allard L F , Szanyi J . Coordinatively unsaturated Al³⁺ centers as binding sites for active catalyst phases of platinum on γ-Al₂O₃. Science, 2009, 325(5948): 1670–1673

[26]	Zhu X Y , Wang T H , Xu Z K , Yue Y Y , Lin M G , Zhu H B . Pt-Sn clusters anchored at Al³⁺ penta sites as a sinter-resistant and regenerable catalyst for propane dehydrogenation. Journal of Energy Chemistry, 2022, 65: 293–301

[27]	Wang J Y , Liu B W , Liu X L , Chong M B , Cheng D G , Chen F Q . Regulation of metal-support interaction by pentacoordinate Al³⁺ content on CeO₂/γ-Al₂O₃ catalyst for oxidative dehydrogenation of cyclohexane. Chinese Journal of Chemical Engineering, 2025, 86: 64–71

[28]	Wang X , Qi G D , Wang Q , Xu J , Deng F . Effect of Pt nanoparticle state on alumina with flexible Al coordination on propane dehydrogenation reactions. Chemistry & Bioengineering, 2024, 41: 16–21

[29]	Zhang Q , Jiang X Z , Su Y , Zhao Y , Qiao B T . Catalytic propane dehydrogenation by anatase supported Ni single-atom catalysts. Chinese Journal of Catalysis, 2024, 57: 105–113

[30]	Li S Y , Mu C L , He N Q , Xu J , Zheng Y P , Chen M S . Surface dynamics of Rh/Al₂O₃ during propane dehydrogenation. Chinese Journal of Catalysis, 2024, 62: 145–155

[31]	Yang F W , Zhang J , Chen J W , Wang G , Yu T , Li Q , Shi Z B , Sun Q S , Zhuo R S , Wang R L . Boosting propane dehydrogenation of defective S-1 stabilized single-atom Pt and ZnO catalysts via coordination environment regulation. Nano Research, 2024, 17(7): 5884–5896

[32]	Zhang W , Wang H Z , Jiang J W , Sui Z J , Zhu Y A , Chen D , Zhou X G . Size dependence of Pt catalysts for propane dehydrogenation: from atomically dispersed to nanoparticles. ACS Catalysis, 2020, 10(21): 12932–12942

[33]	Qiao B T , Wang A Q , Yang X F , Allard L F , Jiang Z , Cui Y T , Liu J Y , Li J , Zhang T . Single-atom catalysis of CO oxidation using Pt1/FeO_x. Nature Chemistry, 2011, 3(8): 634–641

[34]

Bruix A , Rodriguez J A , Ramírez P J , Senanayake S D , Evans J , Park J B , Stacchiola D , Liu P , Hrbek J , Illas F . A new type of strong metal-support interaction and the production of H₂ through the transformation of water on Pt/CeO₂(111) and Pt/CeO_x/TiO₂(110) catalysts. Journal of the American Chemical Society, 2012, 134(21): 8968–8974

[35]	Liu J Y , Duan S B , Xu J , Qiao B T , Lou Y . Catalysis by supported single metal atoms. Microscopy and Microanalysis, 2016, 22(S3): 860–861

[36]	Liu H , Zhang Y , Liu L Y , Chen T X , Zhang X C , Hu P , Xiong C , Zhou J , Zhang H , Dong L H . et al. Platinum clusters stabilized by zincosilicate zeolite for efficient propane dehydrogenation. Chinese Journal of Catalysis, 2025, 71: 208–219

[37]	Hu Z P , Yang D D , Wang Z , Yuan Z Y . State-of-the-art catalysts for direct dehydrogenation of propane to propylene. Chinese Journal of Catalysis, 2019, 40(9): 1233–1254

[38]	Tang Y Q , Chen Y J , Abid A , Meng Z C , Sun X Y , Li B , Zhao Z . Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: double-edged oxygen vacancy. Chinese Journal of Catalysis, 2025, 68: 272–281

[39]	Sun M L , Zhai S X , Weng C C , Wang H Y , Yuan Z Y . Pt-based catalysts for direct propane dehydrogenation: mechanisms revelation, advanced design, and challenges. Molecular Catalysis, 2024, 558: 114029

[40]	Xing Y N , Kang L L , Ma J Y , Jiang Q K , Su Y , Zhang S X , Xu X Y , Li L , Wang A Q , Liu Z P . et al. Sn₁Pt single-atom alloy evolved stable PtSn/nano-Al₂O₃ catalyst for propane dehydrogenation. Chinese Journal of Catalysis, 2023, 48: 164–174

[41]	Xu Z K , Hong H Z , Shen X T , Bao X J , Zhu H B . Advances in the synthesis of durable Pt-zeolite catalysts for propane dehydrogenation. Science China Chemistry, 2026,

[42]	Chen J , Yue Y P , Liu W G . Harnessing light for propane dehydrogenation: a single-atom catalyst milestone achieved under mild conditions. Science China Chemistry, 2025, 68(7): 2776–2778

[43]	Pan T , Wang A X , Cai L , Ding J B , Cao M , Chen W . Effect of Al₂O₃ support properties on activity of propane dehydrogenation catalyst. Petrochemical Technology, 2025, 54(5): 609–617

[44]	Zhai S X , Sun M L , Yang H M , Yuan Z Y . Reducing Pt dependency in propane dehydrogenation: rational design toward efficient and durable catalysts. Chemical Communications, 2026, 62(7): 2178–2198

[45]	Zhao Z C , Xiao D , Chen K Z , Wang R , Liang L X , Liu Z M , Hung I , Gan Z H , Hou G J . Nature of five-coordinated Al in γ-Al₂O₃ revealed by ultra-high-field solid-state NMR. ACS Central Science, 2022, 8(6): 795–803

[46]	Samain L , Jaworski A , Edén M , Ladd D M , Seo D K , Garcia-Garcia F J , Häussermann U . Structural analysis of highly porous γ-Al₂O₃. Journal of Solid State Chemistry, 2014, 217: 1–8

[47]	Yu Y Z , Lei H , Wang L G , Zhang M H . Mechanisms of transforming CHx to CO on Ni(111) surface by density functional theory. Transactions of Tianjin University, 2019, 25(4): 330–339

[48]	Behler J . Four generations of high-dimensional neural network potentials. Chemical Reviews, 2021, 121(16): 10037–10072

[49]	Kang P L , Shang C , Liu Z P . Recent implementations in LASP 3.0: global neural network potential with multiple elements and better long-range description. Chinese Journal of Chemical Physics, 2021, 34(5): 583–590

[50]	Li A M , Cui P , Wang X , Fisher A , Li L Y , Cheng D J . The artificial intelligence-catalyst pipeline: accelerating catalyst innovation from laboratory to industry. Frontiers of Chemical Science and Engineering, 2025, 19(7): 55

[51]	Shang C , Liu Z P . Stochastic surface walking method for structure prediction and pathway searching. Journal of Chemical Theory and Computation, 2013, 9(3): 1838–1845

[52]	Behler J , Parrinello M . Generalized neural-network representation of high-dimensional potential-energy surfaces. Physical Review Letters, 2007, 98(14): 146401

[53]	Huang S D , Shang C , Kang P L , Liu Z P . Atomic structure of boron resolved using machine learning and global sampling. Chemical Science, 2018, 9(46): 8644–8655

[54]	Kresse G , Furthmüller J . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Physical Review B, 1996, 54(16): 11169–11186

[55]	Perdew J P , Burke K , Ernzerhof M . Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868

[56]	Blöchl P E . Projector augmented-wave method. Physical Review B, 1994, 50(24): 17953–17979

[57]	Kresse G , Joubert D . From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 1999, 59(3): 1758–1775

[58]	Monkhorst H J , Pack J D . Special points for Brillouin-zone integrations. Physical Review B, 1976, 13(12): 5188–5192

[59]	BIOVIA, Dassault Systèmes, Materials Studio, version 2022; Dassault Systèmes: San Diego, CA, USA, 2022

[60]	Reuter K, Stampf C, Scheffler M. AB initio atomistic thermodynamics and statistical mechanics of surface properties and functions. Handbook of Materials Modeling: Methods. Dordrecht: Springer, 2005: 149–194

[61]	Henkelman G , Uberuaga B P , Jónsson H . A climbing image nudged elastic band method for finding saddle points and minimum energy paths. The Journal of Chemical Physics, 2000, 113(22): 9901–9904

[62]	Henkelman G , Jónsson H . Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. The Journal of Chemical Physics, 2000, 113(22): 9978–9985

[63]	Yang X , Shang C , Liu Z P . Generalized mechanism for the solid phase transition ofM2O₃ (M = AI, Ga) featuring single cation migration andmartensitic lattice transformation. Chinese Journal of Chemical Physics, 2024, 37(4): 465–470

[64]	Wang Y , Pei C L , Wang X H , Sun G D , Zhao Z J , Gong J L . The role of pentacoordinate Al³⁺ sites of Pt/Al₂O₃ catalysts in propane dehydrogenation. Fundamental Research, 2024, 4(6): 1480–1487

[65]	Zhou R S , Snyder R L . Structures and transformation mechanisms of the η, γ and θ transition aluminas. Acta Crystallographica Section B: Structural Science, 1991, 47(5): 617–630

[66]	Li Z Y , Yang P L , Wu Z L , Fu D L , Zhao Z J , Chen S , Pei C L . Inhibitory effect of water on propane dehydrogenation over metal oxides via dissociative adsorption. Transactions of Tianjin University, 2025, 31(6): 579–589

[67]	Wang Y , Wang X , Qiao M F , Wu Q Y , Liu K L , Yi X D , Qin R X , Fu G , Zheng N F . Color center-rich γ-Al₂O₃ promotes propane dehydrogenation. Science China Chemistry, 2024, 67(12): 4134–4141

[68]	Chen S , Gong J L . A new role of water in propane dehydrogenation. Science China Chemistry, 2025, 68(7): 2784–2785

[69]	Digne M , Sautet P , Raybaud P , Euzen P , Toulhoat H . Hydroxyl groups on γ-alumina surfaces: a DFT study. Journal of Catalysis, 2002, 211(1): 1–5

[70]	Ma Y , Laboratory L B , Huang M Y , Laboratory L B , Chen W X , Laboratory L B , Wang D Q . Tailoring metal-support interaction in Pt/γ-Al₂O₃ single-atom catalyst via surface hydroxylation implicated by DFT calculations. The Journal of Physical Chemistry C, 2025, 129(22): 10329–10342

[71]	Mei D H , Kwak J H , Hu J Z , Cho S J , Szanyi J , Allard L F , Peden C H F . Unique role of anchoring penta-coordinated Al³⁺ sites in the sintering of γ-Al₂O₃-supported Pt catalysts. The Journal of Physical Chemistry Letters, 2010, 1(18): 2688–2691

[72]	Meng Z H , Liao Y , Liu L , Li Y Q , Yan H , Feng X , Chen X B , Liu Y B , Yang C H . Pd⁰–Ov–Ce³⁺ interfacial sites with charge redistribution for enhanced hydrogenation of methyl oleate to methyl stearate. Transactions of Tianjin University, 2024, 30(4): 359–368

[73]	Wang X H , Chen S , Sun G D , Chang X , Tian K G , Zhao Z Y , Wu Z L , Fu D L , Zhao Z J , Pei C L . et al. Decoupling size and electronic effects of Pt through oxygen vacancy engineering in propane dehydrogenation. Science China Chemistry, 2025, 68(11): 6116–6124

[74]	Liu L C , Corma A . Sustainable propane dehydrogenation reaction triggered by strong metal-support interaction. Science China Chemistry, 2025, 68(2): 411–413