Oxygen vacancy-mediated Lewis acid-base pairs on Ce-doped BiOI enable efficient CO₂ conversion

Abstract

CO₂ cycloaddition with epoxides for producing cyclic carbonates is a promising route that aligns with environmental sustainability and economic feasibility. Metal oxyhalides, which contain inherent lattice halogen ions that can act as built-in nucleophiles, offer a distinctive strategy of designing efficient, heterogeneous catalysts for CO₂ cycloaddition. Herein, a series of highly dispersed Ce-doped BiOI (Ce_xBi_1–xOI) catalysts were developed via a one-pot solvothermal method. The introduction of oxyphilic Ce ions enhances the adsorption and activation of epoxides, thus improving the catalytic performance in CO₂ cycloaddition. Experimental characterizations reveal that Ce doping facilitates the formation of oxygen vacancy-mediated Lewis acid-base pairs (Bi–O_v–Ce³⁺···I⁻). In this configuration, the O_v–Ce³⁺···I⁻ strengthens the epoxides adsorption and subsequent epoxy ring-opening, while the Bi–O_v supplies CO₂ adsorbed site. This synergistic interaction reduces the apparent activation energy (70.67 kJ∙mol^–1 for Ce_0.1Bi_0.9OI vs. 108.09 kJ∙mol^–1 for BiOI) of the CO₂ cycloaddition with butylene oxide. Under solvent- and cocatalyst-free conditions, the optimized Ce_0.1Bi_0.9OI catalyst achieved a butylene carbonate yield of 91%. This work provides a feasible strategy for designing efficient catalysts of CO₂ conversion by constructing reinforced synergistic Lewis acid-base sites.

Graphical abstract

Keywords

CO₂ cycloaddition / cyclic carbonates / heterogeneous catalysis / Ce doping / oxygen vacancy

References

[1] Yan T , Liu H , Zeng Z X , Pan W G . Recent progress of catalysts for synthesis of cyclic carbonates from CO₂ and epoxides. Journal of CO₂ Utilization, 2023, 68: 102355

[2] Mishra V , Peter S C . A comprehensive overview of the catalytic pathway for CO₂ utilization with epoxide to cyclic carbonate. Chem Catalysis, 2024, 4(1): 100796

[3] Xu K . Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chemical Reviews, 2004, 104(10): 4303–4418

[4] Huang R , Rintjema J , González-Fabra J , Martín E , Escudero-Adán E C , Bo C , Urakawa A , Kleij A W . Deciphering key intermediates in the transformation of carbon dioxide into heterocyclic products. Nature Catalysis, 2018, 2(1): 62–70

[5] Kamphuis A J , Picchioni F , Pescarmona P P . CO₂-fixation into cyclic and polymeric carbonates: principles and applications. Green Chemistry, 2019, 21(3): 406–448

[6] Martín C , Fiorani G , Kleij A W . Recent advances in the catalytic preparation of cyclic organic carbonates. ACS Catalysis, 2015, 5(2): 1353–1370

[7] Meng X L , Ju Z Y , Zhang S J , Liang X D , von Solms N , Zhang X C , Zhang X P . Efficient transformation of CO₂ to cyclic carbonates using bifunctional protic ionic liquids under mild conditions. Green Chemistry, 2019, 21(12): 3456–3463

[8] Guo L P , Lamb K J , North M . Recent developments in organocatalysed transformations of epoxides and carbon dioxide into cyclic carbonates. Green Chemistry, 2021, 23(1): 77–118

[9] Wang H H , Hou L , Li Y Z , Jiang C Y , Wang Y Y , Zhu Z H . Porous MOF with highly efficient selectivity and chemical conversion for CO₂. ACS Applied Materials & Interfaces, 2017, 9(21): 17969–17976

[10] Yan S , Li W Z , He D F , He G Y , Chen H Q . Recent research progress of metal-organic frameworks (MOFs) based catalysts for CO₂ cycloaddition reaction. Molecular Catalysis, 2023, 550: 113608

[11] Heydari P , Hafizi A , Rajabzadeh M , Karimi M , Khalifeh R , Rahimpour M R . Synthesis and application of nanoporous triple-shelled CuAl₂O₄ hollow sphere catalyst for atmospheric chemical fixation of carbon dioxide. Journal of the Taiwan Institute of Chemical Engineers, 2020, 114: 81–90

[12] Prasad D , Patil K N , Dateer R B , Kim H , Nagaraja B M , Jadhav A H . Basicity controlled MgCo₂O₄ nanostructures as catalyst for viable fixation of CO₂ into epoxides at atmospheric pressure. Chemical Engineering Journal, 2021, 405: 126907

[13] Yuan J C , Fu R F , Wang Z P , Zheng X H , Wang Y C , Yan H , Liu Y B , Qu Y Q , Zhang G Y , Sun B . et al. Engineering interfacial low-coordinated Mg_3C²⁺-O_3C^2– Lewis acid-base pairs on MgO for cycloaddition of CO₂ with epoxides. ACS Catalysis, 2024, 14(14): 11045–11050

[14] Yue C G , Li J X , Wang M Y , Yang Z Y , Xiao T T , Qi J , Huang S Y , Wang Y , He L N , Ma X B . Oxygen vacancy-hydroxyl frustrated Lewis pairs enabling CO₂ cycloaddition for halogen-free synthesis of cyclic carbonates. Green Chemistry, 2025, 27(45): 14531–14539

[15] Wei Y J , Li Y , Xu Y F , Sun Y H , Xu T , Liang H O , Bai J . Crystal facet-dependent CO₂ cycloaddition to epoxides over ZnO catalysts. Frontiers of Chemical Science and Engineering, 2024, 18(5): 53

[16] Wang Y Y , Li S P , Yang Y D , Shen X J , Liu H Z , Han B X . A fully heterogeneous catalyst Br-LDH for the cycloaddition reactions of CO₂ with epoxides. Chemical Communications, 2019, 55(48): 6942–6945

[17] Fierro F , Lamparelli D H , Genga A , Cucciniello R , Capacchione C . I–LDH as a heterogeneous bifunctional catalyst for the conversion of CO₂ into cyclic organic carbonates. Molecular Catalysis, 2023, 538: 112994

[18] Li J X , Yue C G , Ji W H , Feng B M , Wang M Y , Ma X B . Recent advances in cycloaddition of CO₂ with epoxides: halogen-free catalysis and mechanistic insights. Frontiers of Chemical Science and Engineering, 2023, 17(12): 1879–1894

[19] Chen X , Liu Y , Wang G Q , Kuang Y B , Xiang X Q , Di G R , Yin X J , Zhang L , Wang K X , Cai Q Q . et al. Recent advances in photocatalytic CO₂ cycloaddition reaction. Nano Research, 2024, 17(11): 9601–9619

[20] Liu P , Liao Q L , Zhao T X , Yang C L , Shi Y Y , Liu F , Chen Z , Hu X B . Water-resistant defective iMOFs via halogen coordination for CO₂ capture and size-selective cycloaddition. Angewandte Chemie International Edition, 2026, 65(9): e25570

[21] Fu H Y , Wu J W , Liang C H , Chen X . Amine-functionalized metal-organic frameworks loaded with Ag nanoparticles for cycloaddition of CO₂ to epoxides. Frontiers of Chemical Science and Engineering, 2024, 18(11): 126

[22] Hu L H , Xu W , Jiang Q , Ji R Y , Yan Z C , Wu G D . Recent progress on CO₂ cycloaddition with epoxide catalyzed by ZIFs and ZIFs-based materials. Journal of CO₂ Utilization, 2024, 81: 102726

[23] Chen X L , Ok K M . Metal oxyhalides: an emerging family of nonlinear optical materials. Chemical Science, 2022, 13(14): 3942–3956

[24] Wang L , Wang L , Du Y , Xu X , Dou S X . Progress and perspectives of bismuth oxyhalides in catalytic applications. Materials Today Physics, 2021, 16: 100294

[25] Shang S , Shao W , Luo X , Zuo M , Wang H , Zhang X D , Xie Y . Facet engineering in constructing lewis acid-base pairs for CO₂ cycloaddition to high value-added carbonates. Research, 2022, 2022: 9878054

[26] Liu W X , Li L , Shao W , Wang H , Dong Y , Zuo M , Liu J D , Zhang H J , Ye B J , Zhang X D . et al. Vacancy-cluster-mediated surface activation for boosting CO₂ chemical fixation. Chemical Science, 2023, 14(6): 1397–1402

[27] Xia L , Chen H P , Wang W Z , Jia X G , Zhang D K , Wang L , Wu P F , Li L L , Huang J . Facet and dual vacancy engineering-boosting BiOBr for enhanced CO₂ and epoxide cycloaddition reaction under mild and cocatalyst-free conditions: double substrate active sites and activated surface bromine ions synergy. Journal of Materials Science and Technology, 2024, 202: 39–49

[28] Liu H Q , Gu X N , Chen F , Zhang J L. . Preparation of nano BiOCl microsphere and its fabrication mechanism: preparation of nano BiOCl microsphere and its fabrication mechanism.. Chinese Journal of Catalysis, 2011, 32(1): 129–134

[29] Wei X X , Cui B Y , Wang X X , Cao Y Z , Gao L B , Guo S Q , Chen C M . Tuning the physico-chemical properties of BiOBr via solvent adjustment: towards an efficient photocatalyst for water treatment. CrystEngComm, 2019, 21(11): 1750–1757

[30] Shen F Y , Zhang Z H , Wang Z , Ren H , Liang X H , Cai Z J , Yang S T , Sun G D , Cao Y N , Yang X X . et al. Oxophilic Ce single atoms-triggered active sites reverse for superior alkaline hydrogen evolution. Nature Communications, 2024, 15(1): 448

[31] Wang Q D , Zhao C L , Wagemaker M . Rational design of layered oxide materials for batteries. Accounts of Chemical Research, 2025, 58(11): 1742–1753

[32] Wang Q D , Hu Y S , Li H , Cheng H M , Zhao T S , Zhao C L . Ionic potential for battery materials. Nature Reviews Materials, 2025, 10(9): 697–712

[33] Fang X , Yin C J , Chen Z H , Xuan L J , Zhang Z H , Geng X , Lin J , Wu J . Synergizing oxygen vacancy engineering and f-electron doping to promote dynamics of rare-earth-doped bismuth oxyhalides for photocatalysis. Journal of Colloid and Interface Science, 2025, 690: 137311

[34] Kresse G , Furthmüller J . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 1996, 6(1): 15–50

[35] Muhich C L . Re-evaluating CeO₂ expansion upon reduction: noncounterpoised forces, not ionic radius effects, are the cause. Journal of Physical Chemistry C: Nanomaterials and Interfaces, 2017, 121(14): 8052–8059

[36] Vinothkumar G , Rengaraj S , Arunkumar P , Cha S W , Babu K S . Ionic radii and concentration dependency of RE³⁺ (Eu³⁺, Nd³⁺, Pr³⁺, and La³⁺)-doped cerium oxide nanoparticles for enhanced multienzyme-mimetic and hydroxyl radical scavenging activity. Journal of Physical Chemistry C: Nanomaterials and Interfaces, 2019, 123(1): 541–553

[37] Sandhya K , Chitra Priya N S , Rajendran D N , Thappily P . Structural and electrical properties of cerium oxides doped by Sb³⁺ and Bi³⁺ cations. Journal of Electronic Materials, 2020, 49(8): 4936–4944

[38] Bai Z Y , Yang Q , Wang J L . Catalytic ozonation of sulfamethazine using Ce_0.1Fe_0.9OOH as catalyst: mineralization and catalytic mechanisms. Chemical Engineering Journal, 2016, 300: 169–176

[39] Yan S , Peng C , Yang C , Chen Y S , Zhang J B , Guan A X , Lv X M , Wang H Z , Wang Z Q , Sham T K . et al. Electron localization and lattice strain induced by surface lithium doping enable ampere-level electrosynthesis of formate from CO₂. Angewandte Chemie International Edition, 2021, 60(49): 25741–25745

[40] Fan Y M , Jiang S Q , Li Y Z , Zhang Y P , Zhu Y N , Mo S P , Liao L , Zhang Y N , Zhou X B , Zhu Z Q . Ce doping enhances MOF-derived rod shape CoO_x/MnO_x catalysts for photothermocatalytic degradation of 1,2-propanediol and NO without ammonia. Molecular Catalysis, 2026, 589: 115604

[41] Waikar J , More P . Oxygen deficient Ce doped CO supported on alumina catalyst for low-temperature CO oxidation in presence of H₂O and SO₂. Fuel, 2023, 331: 125880

[42] Li Y H , Yin Q , Jia B B , Wang H Q , Gu H F , Hu Q , Yang H S , Guo T Q , Hu P F , Li L D . et al. Boron doping-induced ultrahigh Ce³⁺ ratio in amorphous CeO₂/GO catalyst for low-concentration CO₂ photoreduction. Angewandte Chemie International Edition, 2025, 64(24): e202505668

[43] Wei Y , Xing G C , Liu K , Li G G , Dang P P , Liang S S , Liu M , Cheng Z Y , Jin D Y , Lin J . New strategy for designing orangish-red-emitting phosphor via oxygen-vacancy-induced electronic localization. Light, Science & Applications, 2019, 8(1): 15

[44] Wang Q L , Miao Z R , Zhang Y F , Yan T J , Meng L P , Wang X X . Photocatalytic reduction of CO₂ with H₂O mediated by Ce-tailored bismuth oxybromide surface frustrated Lewis pairs. ACS Catalysis, 2022, 12(7): 4016–4025

[45] Tan Y , Zhou Q , Huang W Y , Lu K Q , Yang K , Chen X J , Li D , Dionysiou D D . Highly efficient photocatalytic degradation over rose-like 1D/2D La(OH)₃/(BiO)₂OHCl heterostructures boosted by rich oxygen vacancies and enhanced interfacial charge transfer. Environmental Science Nano, 2023, 10(1): 215–228

[46] Zaki M I , Hasan M A , Al-Sagheer F A , Pasupulety L . In situ FTIR spectra of pyridine adsorbed on SiO₂-Al₂O₃, TiO₂, ZrO₂, and CeO₂: general considerations for the identification of acid sites on surfaces of finely divided metal oxides. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2001, 190(3): 261–274

[47] Penkova A , Bobadilla L F , Romero-Sarria F , Centeno M A , Odriozola J A . Pyridine adsorption on NiSn/MgO-Al₂O₃: an FTIR spectroscopic study of surface acidity. Applied Surface Science, 2014, 317: 241–251

[48] Wang L , Liu G P , Wang B , Chen X , Wang C T , Lin Z X , Xia J X , Li H M . Oxygen vacancies engineering-mediated BiOBr atomic layers for boosting visible light-driven photocatalytic CO₂ reduction. Solar RRL, 2021, 5(6): 2000480

[49] Ma K L , Wang Z L , Gao W , Chen Y , Li H N , Gao Y , Zhang H M , Ruzimuradov O , Low J , Li Y . Modulating the coordination environment in CeO_2–x towards enhanced photocatalytic CO₂ conversion stability and performance. Advanced Powder Materials, 2026, 5(1): 100362

[50] Lv Y X , Zhang Y J , Shi L , Shi J W , Li J , Li Z H , Ji X , Ma D D , Cheng Y H , Niu C M . Role of oxygen vacancy in rare-earth-free LiCa₃Mg(VO₄)₃ phosphor: enhancing photoluminescence by heat-treatment in oxygen flow. Journal of Materials Science and Technology, 2021, 79: 123–132

[51] Bai J Q , Liu H F , Ma M , Qian Z K , Cai M D , Chen J S , Wu M Y , Wei Y X , Guo L S , Sun S . Comparative study of manganese oxides at different oxidation states for halogen-free synthesis of cyclic carbonate from CO₂ and epoxides. Industrial & Engineering Chemistry Research, 2025, 64(20): 9925–9938

[52] Long G C , Wang A D , Liu X , Li X H , Liu M X , Liu Y , Long J X . Tunable oxygen vacancy clusters enhanced catalytic activity of CeO₂ nanorods on CO₂ cycloaddition. Angewandte Chemie International Edition, 2025, 64(34): e202508217

RIGHTS & PERMISSIONS

Higher Education Press