High-sensitivity formaldehyde gas sensor based on Ce-doped urchin-like SnO₂ nanowires derived from calcination of Sn-MOFs

Abstract

Metal–organic frameworks (MOFs) have attracted widespread attention due to their regular structures, multiple material centers, and various ligands. They are always considered as one kind of ideal templates for developing highly sensitive and selective gas sensors. In this study, the advantages of MOFs with the high specific surface area (71.9891 m²·g⁻¹) and uniform morphology were fully utilized, and urchin-like SnO₂ nanowires were obtained by the hydrothermal method followed by the calcination using Sn-MOFs consisting of the ligand of C₉H₆O₆ (H₃BTC) and Sn/Ce center ions as sacrificial templates. This unique urchin-like nanowire structure facilitated gas diffusion and adsorption, resulting in superior gas sensitivity. A series of Ce-doped SnO₂ nanowires with different doping ratios were synthesized, and their gas sensing properties towards formaldehyde were studied. The resulted Ce-SnO₂ was revealed to have high sensitivity (201.2 at 250 °C), rapid response (4 s), long-term stability, and good repeatability for formaldehyde sensing, and the gas sensing mechanism of Ce-SnO₂ exposed to formaldehyde was also systematically discussed.

Graphical abstract

Keywords

Ce-SnO₂ / SnO₂ / gas sensor / formaldehyde / Sn-MOF

References

[1] Fan G, Nie L, Wang H, . Ce doped SnO/SnO₂ heterojunctions for highly formaldehyde gas sensing at low temperature.Sensors and Actuators B: Chemical, 2022, 373: 132640

[2] Tang Y, Zhao Y, Liu H . Room-temperature semiconductor gas sensors: challenges and opportunities.ACS Sensors, 2022, 7(12): 3582–3597

[3] Reddy C S, Murali G, Reddy A S, . GO incorporated SnO₂ nanotubes as fast response sensors for ethanol vapor in different atmospheres.Journal of Alloys and Compounds, 2020, 813: 152251

[4] Liu Y, Li X, Wang Y, . Hydrothermal synthesis of Au@SnO₂ hierarchical hollow microspheres for ethanol detection.Sensors and Actuators B: Chemical, 2020, 319: 128299

[5] Jeong S Y, Kim J S, Lee J H . Rational design of semiconductor-based chemiresistors and their libraries for next-generation artificial olfaction.Advanced Materials, 2020, 32(51): 2002075

[6] Zhou S, Wang H, Hu J, . Formaldehyde gas sensor with extremely high response employing cobalt-doped SnO₂ ultrafine nanoparticles.Nanoscale Advances, 2022, 4(3): 824–836

[7] Li X B, Luo Z H, Zhang Y, . Excellent sensitivity of SnO₂ nanoparticles to formaldehyde.Modern Physics Letters B, 2022, 36(32N33): 2250176

[8] Feng B, Feng Y, Li Y, . Synthesis of mesoporous Ag₂O/SnO₂ nanospheres for selective sensing of formaldehyde at a low working temperature.ACS Sensors, 2022, 7(12): 3963–3972

[9] Zhang D, Yang Z, Yu S, . Diversiform metal oxide-based hybrid nanostructures for gas sensing with versatile prospects.Coordination Chemistry Reviews, 2020, 413: 213272

[10] Chen H, Li C, Zhang X, . ZnO nanoplates with abundant porosity for significant formaldehyde-sensing.Materials Letters, 2020, 260: 126982

[11] Hwang J Y, Lee Y, Lee G H, . Room-temperature ammonia gas sensing via Au nanoparticle-decorated TiO₂ nanosheets.Discover Nano, 2023, 18(1): 47

[12] Yusof N M, Rozali S, Ibrahim S, . Synthesis of hybridized fireworks-like go-Co₃O₄ nanorods for acetone gas sensing applications.Materials Today. Communications, 2023, 35: 105516

[13] Jian L J, Peng R, He Y Z, . One-step hydrothermal synthesis of urchin-like WO₃ with excellent ammonia gas sensing property.Materials Letters, 2023, 336: 133897

[14] Majhi S M, Navale S T, Mirzaei A, . Strategies to boost chemiresistive sensing performance of In₂O₃-based gas sensors: an overview.Inorganic Chemistry Frontiers, 2023, 10(12): 3428–3467

[15] Zhang H, Ou K, Guan R, . A highly sensitive room-temperature NO₂ gas sensor based on porous MnO₂/rGO hybrid composites.Current Nanoscience, 2023, 19(3): 401–409

[16] Lee J E, Kim D Y, Lee H K, . Sonochemical synthesis of HKUST-1-based CuO decorated with Pt nanoparticles for formaldehyde gas-sensor applications.Sensors and Actuators B: Chemical, 2019, 292: 289–296

[17] Du H, Yang W, Yi W, . Oxygen-plasma-assisted enhanced acetone-sensing properties of ZnO nanofibers by electrospinning.ACS Applied Materials & Interfaces, 2020, 12(20): 23084–23093

[18] Zhang Z R, Wu Y X, Du H Y, . Acetone sensing mechanism of Ar/O₂ plasma modified indium oxide electrospun fibers: a combined DFT and experimental study.Journal of Alloys and Compounds, 2022, 895: 162017

[19] Feng B, Feng Y, Qin J, . Self-template synthesis of spherical mesoporous tin dioxide from tin-polyphenol-formaldehyde polymers for conductometric ethanol gas sensing.Sensors and Actuators B: Chemical, 2021, 341: 129965

[20] Wang H, Qu Y, Li Y, . Effect of Ce³⁺ and Pd²⁺ doping on coral-like nanostructured SnO₂ as acetone gas sensor.Journal of Nanoscience and Nanotechnology, 2013, 13(3): 1858–1862

[21] Li P, Feng B, Feng Y, . Synthesis of mesoporous lanthanum-doped SnO₂ spheres for sensitive and selective detection of the glutaraldehyde disinfectant.ACS Sensors, 2023, 8(10): 3723–3732

[22] Wang G, Yang S, Cao L, . Engineering mesoporous semiconducting metal oxides from metal-organic frameworks for gas sensing.Coordination Chemistry Reviews, 2021, 445: 214086

[23] Li Z, Zhang Y, Cao Y, . Characterization of Sn-MOF and its adsorption application for acid red 3R.Materials Letters, 2021, 282: 128647

[24] Deng Z, Zhang Y, Xu D, . Ultrasensitive formaldehyde sensor based on SnO₂ with rich adsorbed oxygen derived from a metal organic framework.ACS Sensors, 2022, 7(9): 2577–2588

[25] Feng Y Y, Li P, Wei J . Engineering functional mesoporous materials from plant polyphenol based coordination polymers.Coordination Chemistry Reviews, 2022, 468: 214649

[26] Liu J, Xie D, Xu X, . Reversible formation of coordination bonds in Sn-based metal–organic frameworks for high-performance lithium storage.Nature Communications, 2021, 12(1): 3131

[27] Bai S, Liu C, Luo R, . Metal organic frameworks-derived sensing material of SnO₂/NiO composites for detection of triethylamine.Applied Surface Science, 2018, 437: 304–313

[28] Wan G, Zhang F, Xue R, . Ultrasensitive ethanol sensor based on Ce-modified SnO₂ nanoflowers at low temperature.Materials Today. Communications, 2023, 36: 106547

[29] Tan Y, Zhang J . Synergistic effects in bimetallic (Co, Mn)-doped SnO₂ nanobelts for greatly enhanced gas-sensing properties.ACS Applied Materials & Interfaces, 2023, 15(44): 51549–51557

[30] Yu Y, Liu S . Facile synthesis of Ni-doped SnO₂ nanorods and their high gas sensitivity to isopropanol.Frontiers of Materials Science, 2022, 16(1): 220585

[31] Song P, Wang Q, Yang Z . Preparation, characterization and acetone sensing properties of Ce-doped SnO₂ hollow spheres.Sensors and Actuators B: Chemical, 2012, 173: 839–846

[32] Qin W, Xu L, Song J, . Highly enhanced gas sensing properties of porous SnO₂–CeO₂ composite nanofibers prepared by electrospinning.Sensors and Actuators B: Chemical, 2013, 185: 231–237

[33] Jiang Z, Guo Z, Sun B, . Highly sensitive and selective butanone sensors based on cerium-doped SnO₂ thin films.Sensors and Actuators B: Chemical, 2010, 145(2): 667–673

[34] Chen Y, Zhou M, Dong Z, . Enhanced acetone detection performance using facile CeO₂–SnO₂ nanosheets.Applied Physics A: Materials Science & Processing, 2020, 126(1): 33

[35] Zhang Y, Wang C, Zhao L, . Preparation of Ce-doped SnO₂ cuboids with enhanced 2-butanone sensing performance.Sensors and Actuators B: Chemical, 2021, 341: 130039

[36] Zhang X, Liu B, Xu Y, . Facile fabrication of cobalt-doped SnO₂ for gaseous ethanol detection and the catalytic mechanism of cobalt.CrystEngComm, 2019, 21(48): 7528–7534

[37] Wang B J, Ma S Y, Pei S T, . High specific surface area SnO₂ prepared by calcining Sn-MOFs and their formaldehyde-sensing characteristics.Sensors and Actuators B: Chemical, 2020, 321: 128560

[38] Liu L, Liu S . Oxygen vacancies as an efficient strategy for promotion of low concentration SO₂ gas sensing: the case of Au-modified SnO₂.ACS Sustainable Chemistry & Engineering, 2018, 6(10): 13427–13434

[39] Jin L, Zhao X, Qian X, . Nickel nanoparticles encapsulated in porous carbon and carbon nanotube hybrids from bimetallic metal–organic-frameworks for highly efficient adsorption of dyes.Journal of Colloid and Interface Science, 2018, 509: 245–253

[40] Liu K, You H P, Jia G, . Coordination-induced formation of one-dimensional nanostructures of europium benzene-1,3,5-tricarboxylate and its solid-state thermal transformation.Crystal Growth & Design, 2009, 9(8): 3519–3524

[41] Mahalakshmi G, Balachandran V . FT-IR and FT-Raman spectra, normal coordinate analysis and ab initio computations of Trimesic acid.Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 124: 535–547

[42] Lian X, Li Y, Tong X, . Synthesis of Ce-doped SnO₂ nanoparticles and their acetone gas sensing properties.Applied Surface Science, 2017, 407: 447–455

[43] Liu J, Dai M, Wang T, . Enhanced gas sensing properties of SnO₂ hollow spheres decorated with CeO₂ nanoparticles heterostructure composite materials.ACS Applied Materials & Interfaces, 2016, 8(10): 6669–6677

[44] Pacheco-Salazar D G, Aragón F F H, Villegas-Lelovsky L, . Engineering of the band gap induced by Ce surface enrichment in Ce-doped SnO₂ nanocrystals.Applied Surface Science, 2020, 527: 146794

[45] Holzwarth U, Gibson N . The Scherrer equation versus the ‘Debye–Scherrer equation’.Nature Nanotechnology, 2011, 6(9): 534

[46] Liu D, Liu T, Zhang H, . Gas sensing mechanism and properties of Ce-doped SnO₂ sensors for volatile organic compounds.Materials Science in Semiconductor Processing, 2012, 15(4): 438–444

[47] Korsvik C, Patil S, Seal S, . Superoxide dismutase mimetic properties exhibited by vacancy engineered ceria nanoparticles.Chemical Communications, 2007, 10(10): 1056–1058

[48] Feng R, Tian K, Zhang Y, . Recognition of M2 type tumor-associated macrophages with ultrasensitive and biocompatible photoelectrochemical cytosensor based on Ce doped SnO₂/SnS₂ nano heterostructure.Biosensors & Bioelectronics, 2020, 165: 112367

[49] Scalvi L V A, Pineiz T F, Pinheiro M A L, . Resistivity of the film deposited via sol–gel and oxidation state of Ce doping in SnO₂ matrix.Cerâmica, 2011, 57(342): 225–230 (in Portuguese)

[50] Wang D, Zhang M, Chen Z, . Enhanced formaldehyde sensing properties of hollow SnO₂ nanofibers by graphene oxide.Sensors and Actuators B: Chemical, 2017, 250: 533–542

[51] Ding H, Zhu J, Jiang J, . Preparation and gas-sensing property of ultra-fine NiO/SnO₂ nano-particles.RSC Advances, 2012, 2(27): 10324–10329

[52] Zhang G, Han X, Bian W, . Facile synthesis and high formaldehyde-sensing performance of NiO–SnO₂ hybrid nanospheres.RSC Advances, 2016, 6(5): 3919–3926

[53] Meng D, Liu D, Wang G, . Low-temperature formaldehyde gas sensors based on NiO–SnO₂ heterojunction microflowers assembled by thin porous nanosheets.Sensors and Actuators B: Chemical, 2018, 273: 418–428

[54] Zhang R, Gao S, Zhou T, . Facile preparation of hierarchical structure based on p-type Co₃O₄ as toluene detecting sensor.Applied Surface Science, 2020, 503: 144167

[55] Wang J, Hu C, Xia Y, . Mesoporous ZnO nanosheets with rich surface oxygen vacancies for UV-activated methane gas sensing at room temperature.Sensors and Actuators B: Chemical, 2021, 333: 129547

[56] Xing X, Xiao X, Wang L, . Highly sensitive formaldehyde gas sensor based on hierarchically porous Ag-loaded ZnO heterojunction nanocomposites.Sensors and Actuators B: Chemical, 2017, 247: 797–806

[57] Inyawilert K, Wisitsoraat A, Liewhiran C, . H₂ gas sensor based on PdOx-doped In₂O₃ nanoparticles synthesized by flame spray pyrolysis.Applied Surface Science, 2019, 475: 191–203

[58] Chu S, Yang C, Su X . Synthesis of NiO hollow nanospheres via Kirkendall effect and their enhanced gas sensing performance.Applied Surface Science, 2019, 492: 82–88

[59] Wang Y, Liu L, Sun F, . Humidity-insensitive NO₂ sensors based on SnO₂/rGO composites.Frontiers in Chemistry, 2021, 9: 681313

[60] Shu S, Wang M, Yang W, . Synthesis of surface layered hierarchical octahedral-like structured Zn₂SnO₄/SnO₂ with excellent sensing properties toward HCHO.Sensors and Actuators B: Chemical, 2017, 243: 1171–1180

[61] Zhu K, Ma S, Tie Y, . Highly sensitive formaldehyde gas sensors based on Y-doped SnO₂ hierarchical flower-shaped nanostructures.Journal of Alloys and Compounds, 2019, 792: 938–944

[62] Tie Y, Ma S Y, Pei S T, . Pr doped BiFeO₃ hollow nanofibers via electrospinning method as a formaldehyde sensor.Sensors and Actuators B: Chemical, 2020, 308: 127689

[63] Zhang R, Ma S Y, Zhang Q X, . Highly sensitive formaldehyde gas sensors based on Ag doped Zn₂SnO₄/SnO₂ hollow nanospheres.Materials Letters, 2019, 254: 178–181

[64] Gao L, Fu H, Zhu J, . Synthesis of SnO₂ nanoparticles for formaldehyde detection with high sensitivity and good selectivity.Journal of Materials Research, 2020, 35(16): 2208–2217

[65] Huang J, Wang L, Gu C, . Preparation of porous SnO₂ microcubes and their enhanced gas-sensing property.Sensors and Actuators B: Chemical, 2015, 207: 782–790

[66] Sun Y, Wang J, Du H, . Formaldehyde gas sensors based on SnO₂/ZSM-5 zeolite composite nanofibers.Journal of Alloys and Compounds, 2021, 868: 159140

[67] Li X, Zhang N, Liu C, . Enhanced gas sensing properties for formaldehyde based on ZnO/Zn₂SnO₄ composites from one-step hydrothermal synthesis.Journal of Alloys and Compounds, 2021, 850: 156606

[68] Liu J, Zhang L, Cheng B, . A high-response formaldehyde sensor based on fibrous Ag-ZnO/In₂O₃ with multi-level heterojunctions.Journal of Hazardous Materials, 2021, 413: 125352

[69] Das S, Kumar A, Singh J, . Fabrication and modeling of laser ablated NiO nanoparticles decorated SnO₂ based formaldehyde sensor.Sensors and Actuators B: Chemical, 2023, 387: 133824

Declaration of competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the 11th Graduate Innovative Fund of Wuhan Institute of Technology (Grant No. CX2019176).

Online appendix

Electronic supplementary material (ESM) can be found in the online version at https://doi.org/10.1007/s11706-024-0676-x and https://journal.hep.com.cn/foms/EN/10.1007/s11706-024-0676-x that includes Figs. S1–S3.

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