Crystal facet-dependent CO₂ cycloaddition to epoxides over ZnO catalysts

Abstract

With regard to green chemistry and sustainable development, the fixation of CO₂ into epoxides to form cyclic carbonates is an attractive and promising pathway for CO₂ utilization. Metal oxides, renowned as promising eco-friendly catalysts for industrial production, are often undervalued in terms of their impact on the CO₂ addition reaction. In this work, we successfully developed ZnO nanoplates with (002) surfaces and ZnO nanorods with (100) surfaces via morphology-oriented regulation to explore the effect of crystal faces on CO₂ cycloaddition. The quantitative data obtained from electron paramagnetic resonance spectroscopy indicated that the concentration of oxygen vacancies on the ZnO nanoplate surfaces was more than twice that on the ZnO nanorod surfaces. Density functional theory calculations suggested that the (002) surfaces have lower adsorption energies for CO₂ and epichlorohydrin than the (100) surfaces. As a result, the yield of cyclochloropropene carbonate on the ZnO nanoplates (64.7%) was much greater than that on the ZnO nanorods (42.3%). Further evaluation of the reused catalysts revealed that the decrease in the oxygen vacancy concentration was the primary factor contributing to the decrease in catalytic performance. Based on these findings, a possible catalytic mechanism for CO₂ cycloaddition with epichlorohydrin was proposed. This work provides a new idea for the controllable preparation of high-performance ZnO catalysts for the synthesis of cyclic carbonates from CO₂ and epoxides.

Graphical abstract

Keywords

carbon dioxide / cycloaddition / zinc oxide / crystal face / oxygen vacancy

References

[1] Bierbaumer S , Nattermann M , Schulz L , Zschoche R , Erb T J , Winkler C K , Tinzl M , Glueck S M . Enzymatic conversion of CO₂: from natural to artificial utilization. Chemical Reviews, 2023, 123(9): 5702–5754

[2] Ren J , Lou H , Xu N , Zeng F , Pei G , Wang Z . Methanation of CO/CO₂ for power to methane process: fundamentals, status, and perspectives. Journal of Energy Chemistry, 2023, 80: 182–206

[3] Liu X , Bai S , Zhuang H , Yan Z . Preparation of Cu/ZrO₂ catalysts for methanol synthesis from CO₂/H₂. Frontiers of Chemical Science and Engineering, 2012, 6(1): 47–52

[4] Zhang X , Wang J , Song Z , Zhao X , Sun J , Mao Y , Wang W . Co₃O₄–CeO₂ for enhanced syngas by low-temperature methane conversion with C utilization via a catalytic chemical looping process. Fuel Processing Technology, 2023, 245: 107741

[5] Liu S , Zhao Q , Han X , Wei C , Liang H , Wang Y , Huang S , Ma X . Proximity effect of Fe–Zn bimetallic catalysts on CO₂ hydrogenation performance. Transactions of Tianjin University, 2023, 29(4): 293–303

[6] Kilic A , Sobay B , Aytar E , Söylemez R . Synthesis and effective catalytic performance in cycloaddition reactions with CO₂ of boronate esters versus N-heterocyclic carbene (NHC)-stabilized boronate esters. Sustainable Energy & Fuels, 2020, 4(11): 5682–5696

[7] Li J , Yue C , Ji W , Feng B , Wang M Y , Ma X . 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

[8] Zeng Y Y , Qiao L Y , Zong S S , Guo R , Cheng J K , Cao X Y , Zhou Z F , Fan M H , Yao Y G . Dispersed Pd/alumina catalyst with finite iodine entry for boosted CO purification and dimethyl carbonate synthesis. Chemical Engineering Journal, 2023, 466: 143348

[9] Kilic A , Yasar E , Aytar E . Neutral boron [(L_1–3)BPh₂] and cationic charged boron [(L_1a–3a)BPh₂] complexes for chemical CO₂ conversion to obtain cyclic carbonates under ambient conditions. Sustainable Energy & Fuels, 2019, 3(4): 1066–1077

[10] Andrea K A , Kerton F M . Triarylborane-catalyzed formation of cyclic organic carbonates and polycarbonates. ACS Catalysis, 2019, 9(3): 1799–1809

[11] Ansari I , Singh P , Mittal A , Mahato R I , Chitkara D . 2,2-Bis(hydroxymethyl) propionic acid based cyclic carbonate monomers and their (co)polymers as advanced materials for biomedical applications. Biomaterials, 2021, 275: 120953

[12] Su C C , He M , Amine R , Chen Z , Sahore R , Dietz Rago N , Amine K . Cyclic carbonate for highly stable cycling of high voltage lithium metal batteries. Energy Storage Materials, 2019, 17: 284–292

[13] Wu K , Su T , Hao D , Liao W , Zhao Y , Ren W , Deng C , Lu H . Choline chloride-based deep eutectic solvents for efficient cycloaddition of CO₂ with propylene oxide. Chemical Communications, 2018, 54(69): 9579–9582

[14] Wang R , Liu G , Kim S K , Bowen K H , Zhang X . Gas-phase CO₂ activation with single electrons, metal atoms, clusters, and molecules. Journal of Energy Chemistry, 2021, 63: 130–137

[15] Wang P , Lv Q , Tao Y , Cheng L , Li R , Jiao Y , Fang C , Li H , Geng C , Sun C . . One-pot efficient fixation of low-concentration CO₂ into cyclic carbonate by mesoporous pyridine-functionalized binuclear poly(ionic liquid)s. Molecular Catalysis, 2023, 544: 113157

[16] Alhafez A , Aytar E , Kilic A . Enhancing catalytic strategy for cyclic carbonates synthesized from CO₂ and epoxides by using cobaloxime-based double complex salts as catalysts. Journal of CO₂ Utilization, 2022, 63: 102129

[17] Kilic A , Alhafez A , Aytar E , Soylemez R . The sustainable catalytic conversion of CO₂ into value-added chemicals by using cobaloxime-based double complex salts as efficient and solvent-free catalysts. Inorganica Chimica Acta, 2023, 554: 121547

[18] Chen Y , Yu J , Yang Y , Huo F , Li C . A continuous process for cyclic carbonate synthesis from CO₂ catalyzed by the ionic liquid in a microreactor system: reaction kinetics, mass transfer, and process optimization. Chemical Engineering Journal, 2023, 455: 140670

[19] Aggrawal S , Sharma R , Mohanty P . CuO immobilized paper matrices: a green catalyst for conversion of CO₂ to cyclic carbonates. Journal of CO₂ Utilization, 2021, 46: 101466

[20] Shen Q , Yan H , Yuan X , Li R , Kong D , Zhang W , Zhang H , Liu Y , Chen X , Feng X . . Tailoring morphology of MgO catalyst for the enhanced coupling reaction of CO₂ and glycerol to glycerol carbonate. Fuel, 2023, 335: 126972

[21] Dai W , Luo S , Yin S , Au C . A mini review on chemical fixation of CO₂: absorption and catalytic conversion into cyclic carbonates. Frontiers of Chemical Engineering in China, 2010, 4(2): 163–171

[22] Zhong S , Liang L , Liu M , Liu B , Sun J . DMF and mesoporous Zn/SBA-15 as synergistic catalysts for the cycloaddition of CO₂ to propylene oxide. Journal of CO₂ Utilization, 2015, 9: 58–65

[23] Zhang H , Si S , Zhai G , Li Y , Liu Y , Cheng H , Wang Z , Wang P , Zheng Z , Dai Y . . The long-distance charge transfer process in ferrocene-based MOFs with FeO₆ clusters boosts photocatalytic CO₂ chemical fixation. Applied Catalysis B: Environmental, 2023, 337: 122909

[24] Cheng R , Wang A , Sang S , Liang H , Liu S , Tsiakaras P . Photocatalytic CO₂ cycloaddition over highly efficient W₁₈O₄₉-based composites: an economic and ecofriendly choice. Chemical Engineering Journal, 2023, 466: 142982

[25] Yano T , Matsui H , Koike T , Ishiguro H , Fujihara H , Yoshihara M , Maeshima T . Magnesium oxide-catalysed reaction of carbon dioxide with an epoxide with retention of stereochemistry. Chemical Communications, 1997, 12(12): 1129–1130

[26] Sahoo A , Chowdhury A H , Singha P , Banerjee A , Islam S M , Bala T . Morphology of ZnO triggered versatile catalytic reactions towards CO₂ fixation and acylation of amines at optimized reaction conditions. Molecular Catalysis, 2020, 493: 111070

[27] Dai W , Zou M , Long J , Li B , Zhang S , Yang L , Wang D , Mao P , Luo S , Luo X . Nanoporous N-doped carbon/ZnO hybrid derived from zinc aspartate: an acid-base bifunctional catalyst for efficient fixation of carbon dioxide into cyclic carbonates. Applied Surface Science, 2021, 540: 148311

[28] Zhang T T , Zhang B S , Li L , Zhao N , Xiao F K . Zn–Mg mixed oxide as high-efficiency catalyst for the synthesis of propylene carbonate by urea alcoholysis. Catalysis Communications, 2015, 66: 38–41

[29] Park C , Park J E , Choi H C . Crystallization-induced properties from morphology-controlled organic crystals. Accounts of Chemical Research, 2014, 47(8): 2353–2364

[30] Martínez-Suárez L , Siemer N , Frenzel J , Marx D . Reaction network of methanol synthesis over Cu/ZnO nanocatalysts. ACS Catalysis, 2015, 5(7): 4201–4218

[31] Chen Y , Dai Q , Zhang Q , Huang Y . Precisely deposited Pd on ZnO (002) surfacets derived from complex reduction strategy for methanol steam reforming. International Journal of Hydrogen Energy, 2022, 47(33): 14869–14883

[32] Goktas A , Modanlı S , Tumbul A , Kilic A . Facile synthesis and characterization of ZnO, ZnO:Co, and ZnO/ZnO: Co nano rod-like homojunction thin films: role of crystallite/grain size and microstrain in photocatalytic performance. Journal of Alloys and Compounds, 2022, 893: 162334

[33] Tumbul A , Aslan F , Demirozu S , Goktas A , Kilic A , Durgun M , Zarbali M Z . Solution processed boron doped ZnO thin films: influence of different boron complexes. Materials Research Express, 2018, 6(3): 035903

[34] Mclaren A , Valdes-Solis T , Li G , Tsang S C . Shape and size effects of ZnO nanocrystals on photocatalytic activity. Journal of the American Chemical Society, 2009, 131(35): 12540–12541

[35] Chen H , Cui H , Lv Y , Liu P , Hao F , Xiong W , Luo H . CO₂ hydrogenation to methanol over Cu/ZnO/ZrO₂ catalysts: effects of ZnO morphology and oxygen vacancy. Fuel, 2022, 314: 123035

[36] Chai M Q , Tan Y , Pei G X , Li L , Zhang L , Liu X Y , Wang A , Zhang T . Crystal plane effect of ZnO on the catalytic activity of gold nanoparticles for the acetylene hydrogenation reaction. Journal of Physical Chemistry C, 2017, 121(36): 19727–19734

[37] Liu W , Liu H , Liu Y , Dong Z , Luo L . Surface plane effect of ZnO on the catalytic performance of Au/ZnO for the CO oxidation reaction. Journal of Physical Chemistry C, 2022, 126(33): 14155–14162

[38] Iglesias-Juez A , Viñes F , Lamiel García O , Fernández García M , Illas F . Morphology effects in photoactive ZnO nanostructures: photooxidative activity of polar surfaces. Journal of Materials Chemistry A, 2015, 3(16): 8782–8792

[39] Wu G , Zhao G , Sun J , Cao X , He Y , Feng J , Li D . The effect of oxygen vacancies in ZnO at an Au/ZnO interface on its catalytic selective oxidation of glycerol. Journal of Catalysis, 2019, 377: 271–282

[40] Ghosh M , Ghosh S , Seibt M , Rao K Y , Peretzki P , Mohan Rao G . Ferroelectric origin in one-dimensional undoped ZnO towards high electromechanical response. CrystEngComm, 2016, 18(4): 622–630

[41] Niu L , Hong S , Wang M . Properties of ZnO with oxygen vacancies and its application in humidity sensor. Journal of Electronic Materials, 2021, 50(8): 4480–4487

[42] Zhu M , Zhang Z , Zhong M , Tariq M , Li Y , Li W , Jin H , Skotnicova K , Li Y . Oxygen vacancy induced ferromagnetism in Cu-doped ZnO. Ceramics International, 2017, 43(3): 3166–3170

[43] Huang C , Wen J , Sun Y , Zhang M , Bao Y , Zhang Y , Liang L , Fu M , Wu J , Ye D . . CO₂ hydrogenation to methanol over Cu/ZnO plate model catalyst: effects of reducing gas induced Cu nanoparticle morphology. Chemical Engineering Journal, 2019, 374: 221–230

[44] Wang J , Xia Y , Dong Y , Chen R , Xiang L , Komarneni S . Defect-rich ZnO nanosheets of high surface area as an efficient visible-light photocatalyst. Applied Catalysis B: Environmental, 2016, 192: 8–16

[45] Ren Q , Yang K , Liu F , Yao M , Ma J , Geng S , Cao J . Role of the structure and morphology of zirconia in ZnO/ZrO₂ catalyst for CO₂ hydrogenation to methanol. Molecular Catalysis, 2023, 547: 113280

[46] Liu M H , Chen Y W , Lin T S , Mou C Y . Defective mesocrystal ZnO-supported gold catalysts: facilitating CO oxidation via vacancy defects in ZnO. ACS Catalysis, 2018, 8(8): 6862–6869

[47] Li G R , Hu T , Pan G L , Yan T Y , Gao X P , Zhu H Y . Morphology-function relationship of ZnO: polar planes, oxygen vacancies, and activity. Journal of Physical Chemistry C, 2008, 112(31): 11859–11864

[48] Zhou J , Yang S , Wan W , Chen L , Chen J . Synergistic catalysis of mesoporous Cu/Co₃O₄ and surface oxygen vacancy for CO₂ fixation to carbamates. Journal of Catalysis, 2023, 418: 178–189

[49] Lu S , Song H , Xiao Y , Qadir K , Li Y , Li Y , He G . Promoted catalytic activity of CO oxidation at low temperatures by tuning ZnO morphology for optimized CuO/ZnO catalysts. Colloid and Interface Science Communications, 2023, 52: 100698

[50] Hsieh P T , Chen Y C , Kao K S , Wang C M . Luminescence mechanism of ZnO thin film investigated by XPS measurement. Applied Physics A, 2007, 90(2): 317–321

[51] Kilic A , Aytar E , Beyazsakal L . A novel dopamine-based boronate esters with the organic base as highly efficient, stable, and green catalysts for the conversion of CO₂ with epoxides to cyclic carbonates. Energy Technology, 2021, 9(9): 2100478

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 22008177), the Natural Science Foundation of Inner Mongolia (Grant Nos. 2023MS02004 and 2023MS02011), the Foundation of Inner Mongolia Education Department (Grant No. JY20220266), and the Program for Young Talents of Science and Technology of Inner Mongolia (Grant No. NJYT23040).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2412-6 and is accessible for authorized users.

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