On-Chip Construction of Hierarchically Macro-/Mesoporous Cerium Oxide/Pt Gas Sensitive Film for Ultrasensitive Detection of Trace Oxygen

Yu Deng , Keyu Chen , Wenhe Xie , Xin-Yu Huang , Fengluan Jiang , Lingxiao Xue , Ziling Zhang , Qin Yue , Limin Wu , Wei Luo , Yonghui Deng

Interdisciplinary Materials ›› 2025, Vol. 4 ›› Issue (4) : 585 -598.

PDF
Interdisciplinary Materials ›› 2025, Vol. 4 ›› Issue (4) :585 -598. DOI: 10.1002/idm2.12254
RESEARCH ARTICLE

On-Chip Construction of Hierarchically Macro-/Mesoporous Cerium Oxide/Pt Gas Sensitive Film for Ultrasensitive Detection of Trace Oxygen

Author information +
History +
PDF

Abstract

Hierarchically porous structure is extremely favorable for many applications, including heterogeneous catalysis, chemical sensing, and energy conversion and storage. In these applications, controllable synthesis and assembly of transition metal oxide materials with tailored hierarchically porous structure and chemical microenvironments are highly desired but challenging. Herein, uniform mesoporous cerium oxide (mCeO2) microspheres functionalized with Pt nanoparticles (NPs) were designed via efficient nanoemulsion approach and used to construct hierarchical macro-/mesoporous CeO2/Pt film on micro-electromechanical system (MEMS) chips. The resultant functional chip-based devices have controllable porous structure and rich highly accessible active Pt–CeO2 interfaces, and thus they exhibit outstanding performance as oxygen sensors with an unprecedented low limit of detection (LOD, 7.16 ppm), high sensitivity at a relatively low working temperature (250°C). Finite element analysis, density functional theory calculations, and in situ characterizations reveal that, such an excellent performance is mainly due to the favorable mass transfer and gas–solid interface interaction, the oxygen spillover effect enabled by the nanosized Pt, and the enhanced catalytic reaction causing the dramatic change of electronic resistance of the sensing layer in oxygen atmosphere. Finally, a smart gas sensing module capable of real-time precise detection of oxygen was fabricated, demonstrating the possibility for commercial application.

Keywords

cerium oxide / hierarchically porous structure / mesoporous materials / oxygen sensor / sensing mechanism

Cite this article

Download citation ▾
Yu Deng, Keyu Chen, Wenhe Xie, Xin-Yu Huang, Fengluan Jiang, Lingxiao Xue, Ziling Zhang, Qin Yue, Limin Wu, Wei Luo, Yonghui Deng. On-Chip Construction of Hierarchically Macro-/Mesoporous Cerium Oxide/Pt Gas Sensitive Film for Ultrasensitive Detection of Trace Oxygen. Interdisciplinary Materials, 2025, 4(4): 585-598 DOI:10.1002/idm2.12254

登录浏览全文

4963

注册一个新账户 忘记密码

References

[1]

P. Gallipoli and B. J. P. Huntly, “Histone Modifiers Are Oxygen Sensors,” Science 363 (2019): 1148–1149.

[2]

C. Shan, S. Yao, and M. Driess, “Where Silylene–Silicon Centres Matter in the Activation of Small Molecules,” Chemical Society Reviews 49 (2020): 6733–6754.

[3]

M.-A. Stoeckel, M. Gobbi, S. Bonacchi, et al., “Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite,” Advanced Materials 29 (2017): 1702469.

[4]

H. Zhu and H. F. Bunn, “How Do Cells Sense Oxygen?,” Science 292 (2001): 449–451.

[5]

D. J. Wales, J. Grand, V. P. Ting, et al., “Gas Sensing Using Porous Materials for Automotive Applications,” Chemical Society Reviews 44 (2015): 4290–4321.

[6]

S. Michele and C. Davide, “Oxygen Administration During General Anaesthesia for Surgery,” BMJ 379 (2022): o2823.

[7]

P. Wilmshurst, “ABC of Oxygen,” BMJ 317 (1998): 996–999.

[8]

E. Roussakis, Z. Li, A. J. Nichols, and C. L. Evans, “Oxygen-Sensing Methods in Biomedicine From the Macroscale to the Microscale,” Angewandte Chemie International Edition 54 (2015): 8340–8362.

[9]

K. Jasek, M. Pasternak, and M. Grabka, “Paramagnetic Sensors for the Determination of Oxygen Concentration in Gas Mixtures,” ACS Sensors 7 (2022): 3228–3242.

[10]

Z. Wu, Q. Ding, and H. Wang, et al., “A Humidity-Resistant, Sensitive, and Stretchable Hydrogel-Based Oxygen Sensor for Wireless Health and Environmental Monitoring,” Advanced Functional Materials 34 (2023): 2308280.

[11]

J. Zhao, B. Qin, L. Liu, et al., “Enhanced Low-Temperature Response of Ga2O3-Based Oxygen Sensor by Modulating the Surficial Micro-Nano Structures,” Sensors and Actuators B: Chemical 378 (2023): 133180.

[12]

A. Sharma, S. B. Eadi, H. Noothalapati, M. Otyepka, H.-D. Lee, and K. Jayaramulu, “Porous Materials as Effective Chemiresistive Gas Sensors,” Chemical Society Reviews 53 (2024): 2530–2577.

[13]

X. Yang, Y. Deng, H. Yang, et al., “Functionalization of Mesoporous Semiconductor Metal Oxides for Gas Sensing: Recent Advances and Emerging Challenges,” Advanced Science 10 (2023): 2204810.

[14]

S. Zhou, Y. Zhao, Y. Xun, et al., “Programmable and Modularized Gas Sensor Integrated by 3D Printing,” Chemical Reviews 124 (2024): 3608–3643.

[15]

W. P. Sari, C. Blackman, Y. Zhu, and J. Covington, “Deposition of Tungsten Oxide and Silver Decorated Tungsten Oxide for Use in Oxygen Gas Sensing,” 2017 IEEE Sensors, 2017: 1–3.

[16]

L. Yao, G. Ou, W. Liu, X. Zhao, H. Nishijima, and W. Pan, “Fabrication of High Performance Oxygen Sensors Using Multilayer Oxides With High Interfacial Conductivity,” Journal of Materials Chemistry A 4 (2016): 11422–11429.

[17]

L. Yang, H. Xiao, Y. Qian, et al., “Bioinspired Hierarchical Porous Membrane for Efficient Uranium Extraction From Seawater,” Nature Sustainability 5 (2022): 71–80.

[18]

D. Nepal, S. Kang, K. M. Adstedt, et al., “Hierarchically Structured Bioinspired Nanocomposites,” Nature Materials 22 (2023): 18–35.

[19]

J. Yi, G. Zou, J. Huang, et al., “Water-Responsive Supercontractile Polymer Films for Bioelectronic Interfaces,” Nature 624 (2023): 295–302.

[20]

X. Xie, Y. Huang, Z. Yang, A. Li, and X. Zhang, “Diatom Cribellum-Inspired Hierarchical Metamaterials: Unifying Perfect Absorption Toward Subwavelength Color Printing,” Advanced Materials 36 (2024): 2470260.

[21]

C.-T. Hung, L. Duan, T. Zhao, et al., “Gradient Hierarchically Porous Structure for Rapid Capillary-Assisted Catalysis,” Journal of the American Chemical Society 144 (2022): 6091–6099.

[22]

Z. Liu, W. Li, W. Sheng, et al., “Tunable Hierarchically Structured Meso-Macroporous Carbon Spheres From a Solvent-Mediated Polymerization-Induced Self-Assembly,” Journal of the American Chemical Society 145 (2023): 5310–5319.

[23]

L. Hu, W.-I. Lee, S. Roy, et al., “Hierarchically Porous and Single Zn Atom-Embedded Carbon Molecular Sieves for H2 Separations,” Nature Communications 15 (2024): 5688.

[24]

X.-Y. Yang, L.-H. Chen, Y. Li, J. C. Rooke, C. Sanchez, and B.-L. Su, “Hierarchically Porous Materials: Synthesis Strategies and Structure Design,” Chemical Society Reviews 46 (2017): 481–558.

[25]

G. Karniadakis, A. Beskok, and A. Nr, MicroFlows and Nanoflows—Fundamentals and Simulation (2005).

[26]

M. Tiemann, “Porous Metal Oxides as Gas Sensors,” Chemistry—A European Journal 13 (2007): 8376–8388.

[27]

C. Yuan, J. Ma, Y. Zou, et al., “Modeling Interfacial Interaction Between Gas Molecules and Semiconductor Metal Oxides: A New View Angle on Gas Sensing,” Advanced Science 9 (2022): 2203594.

[28]

J. Hwang, C. Jo, K. Hur, J. Lim, S. Kim, and J. Lee, “Direct Access to Hierarchically Porous Inorganic Oxide Materials With Three-Dimensionally Interconnected Networks,” Journal of the American Chemical Society 136 (2014): 16066–16072.

[29]

C. Jo, J. Hwang, W.-G. Lim, J. Lim, K. Hur, and J. Lee, “Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides,” Advanced Materials 30 (2018): 1703829.

[30]

Z.-L. Wang, K. Sun, J. Henzie, et al., “Spatially Confined Assembly of Monodisperse Ruthenium Nanoclusters in a Hierarchically Ordered Carbon Electrode for Efficient Hydrogen Evolution,” Angewandte Chemie International Edition 57 (2018): 5848–5852.

[31]

J. Han, H. Xu, B. Zhao, et al., “‘Hard’ Emulsion-Induced Interface Super-Assembly: A General Strategy for Two-Dimensional Hierarchically Porous Metal–Organic Framework Nanoarchitectures,” Journal of the American Chemical Society 146 (2024): 18979–18988.

[32]

K. W. Tan, B. Jung, J. G. Werner, E. R. Rhoades, M. O. Thompson, and U. Wiesner, “Transient Laser Heating Induced Hierarchical Porous Structures From Block Copolymer-Directed Self-Assembly,” Science 349 (2015): 54–58.

[33]

O. Guselnikova, A. Trelin, Y. Kang, et al., “Pretreatment-Free SERS Sensing of Microplastics Using a Self-Attention-Based Neural Network on Hierarchically Porous Ag Foams,” Nature Communications 15 (2024): 4351.

[34]

Z. Li, Q. Fan, and Y. Yin, “Colloidal Self-Assembly Approaches to Smart Nanostructured Materials,” Chemical Reviews 122 (2022): 4976–5067.

[35]

M. Wang, Z. Yan, T. Wang, et al., “Gesture Recognition Using a Bioinspired Learning Architecture That Integrates Visual Data With Somatosensory Data From Stretchable Sensors,” Nature Electronics 3 (2020): 563–570.

[36]

D. Periyanagounder, T.-C. Wei, T.-Y. Li, et al., “Fast-Response, Highly Air-Stable, and Water-Resistant Organic Photodetectors Based on a Single-Crystal Pt Complex,” Advanced Materials 32 (2020): 1904634.

[37]

C. T. Campbell and C. H. F. Peden, “Oxygen Vacancies and Catalysis on Ceria Surfaces,” Science 309 (2005): 713–714.

[38]

T. Montini, M. Melchionna, M. Monai, and P. Fornasiero, “Fundamentals and Catalytic Applications of CeO2-Based Materials,” Chemical Reviews 116 (2016): 5987–6041.

[39]

N. Fu, X. Liang, X. Wang, et al., “Controllable Conversion of Platinum Nanoparticles to Single Atoms in Pt/CeO2 by Laser Ablation for Efficient CO Oxidation,” Journal of the American Chemical Society 145 (2023): 9540–9547.

[40]

J. Park, S. Lee, H.-E. Kim, et al., “Investigation of the Support Effect in Atomically Dispersed Pt on WO3−x for Utilization of Pt in the Hydrogen Evolution Reaction,” Angewandte Chemie International Edition 58 (2019): 16038–16042.

[41]

J. Chen, S. Xiong, H. Liu, et al., “Reverse Oxygen Spillover Triggered by CO Adsorption on Sn-Doped Pt/TiO2 for Low-Temperature CO Oxidation,” Nature Communications 14 (2023): 3477.

[42]

M. Gao, Z. Yang, H. Zhang, et al., “Ordered Mesopore Confined Pt Nanoclusters Enable Unusual Self-Enhancing Catalysis,” ACS Central Science 8 (2022): 1633–1645.

[43]

H. Yu, W. Wang, M. Liu, et al., “Versatile Synthesis of Dendritic Mesoporous Rare Earth-based Nanoparticles,” Science Advances 8 (2022): eabq2356.

[44]

Y. Ma, Y. Zhang, X. Wang, et al., “A Chelation-Induced Cooperative Self-Assembly Methodology for the Synthesis of Mesoporous Metal Hydroxide and Oxide Nanospheres,” Nanoscale 10 (2018): 5731–5737.

[45]

L. Peng, H. Peng, Y. Liu, et al., “Spiral Self-Assembly of Lamellar Micelles Into Multi-Shelled Hollow Nanospheres With Unique Chiral Architecture,” Science Advances 7 (2021): eabi7403.

[46]

B. Y. Guan, S. L. Zhang, and X. W. Lou, “Realization of Walnut-Shaped Particles With Macro-/Mesoporous Open Channels Through Pore Architecture Manipulation and Their Use in Electrocatalytic Oxygen Reduction,” Angewandte Chemie International Edition 57 (2018): 6176–6180.

[47]

R. F. André, G. Rousse, C. Sassoye, et al., “From Ce(OH)3 to Nanoscaled CeO2: Identification and Crystal Structure of a Cerium Oxyhydroxide Intermediate Phase,” Chemistry of Materials 35 (2023): 5040–5048.

[48]

X. Ding, Y. Yang, Z. Li, et al., “Engineering a Nickel–Oxygen Vacancy Interface for Enhanced Dry Reforming of Methane: A Promoted Effect of CeO2 Introduction Into Ni/MgO,” ACS Catalysis 13 (2023): 15535–15545.

[49]

A. Xu, T. Liu, D. Liu, et al., “Edge-Rich Pt−O−Ce Sites in CeO2 Supported Patchy Atomic-Layer Pt Enable a Non-CO Pathway for Efficient Methanol Oxidation,” Angewandte Chemie International Edition 63 (2024): e202410545.

[50]

H. Sun, H. Wang, and Z. Qu, “Construction of CuO/CeO2 Catalysts via the Ceria Shape Effect for Selective Catalytic Oxidation of Ammonia,” ACS Catalysis 13 (2023): 1077–1088.

[51]

Y. Li, W. Luo, N. Qin, et al., “Highly Ordered Mesoporous Tungsten Oxides With a Large Pore Size and Crystalline Framework for H2S Sensing,” Angewandte Chemie International Edition 53 (2014): 9035–9040.

[52]

J. Lee, M. Christopher Orilall, S. C. Warren, M. Kamperman, F. J. DiSalvo, and U. Wiesner, “Direct Access to Thermally Stable and Highly Crystalline Mesoporous Transition-metal Oxides With Uniform Pores,” Nature Materials 7 (2008): 222–228.

[53]

T. T. Phan, T. Tosa, and Y. Majima, “20-nm-Nanogap Oxygen Gas Sensor With Solution-Processed Cerium Oxide,” Sensors and Actuators B: Chemical 343 (2021): 130098.

[54]

J. Ma, Y. Ren, X. Zhou, et al., “Pt Nanoparticles Sensitized Ordered Mesoporous WO3 Semiconductor: Gas Sensing Performance and Mechanism Study,” Advanced Functional Materials 28 (2018): 1705268.

[55]

P. Makuła, M. Pacia, and W. Macyk, “How to Correctly Determine the Band Gap Energy of Modified Semiconductor Photocatalysts Based on UV–Vis Spectra,” Journal of Physical Chemistry Letters 9 (2018): 6814–6817.

[56]

M. E. Khan, M. M. Khan, and M. H. Cho, “Ce3+-ion, Surface Oxygen Vacancy, and Visible Light-induced Photocatalytic Dye Degradation and Photocapacitive Performance of CeO2-Graphene Nanostructures,” Scientific Reports 7 (2017): 5928.

[57]

K. Chen, W. Xie, Y. Deng, et al., “Alkaloid Precipitant Reaction Inspired Controllable Synthesis of Mesoporous Tungsten Oxide Spheres for Biomarker Sensing,” ACS Nano 17 (2023): 15763–15775.

[58]

B. Khan, M. B. Faheem, K. Peramaiah, et al., “Unassisted Photoelectrochemical CO2-to-Liquid Fuel Splitting Over 12% Solar Conversion Efficiency,” Nature Communications 15 (2024): 6990.

[59]

Z. Song, W. Ye, Z. Chen, et al., “Wireless Self-Powered High-Performance Integrated Nanostructured-Gas-Sensor Network for Future Smart Homes,” ACS Nano 15 (2021): 7659–7667.

[60]

Z. Hu, X. Liu, D. Meng, Y. Guo, Y. Guo, and G. Lu, “Effect of Ceria Crystal Plane on the Physicochemical and Catalytic Properties of Pd/Ceria for CO and Propane Oxidation,” ACS Catalysis 6 (2016): 2265–2279.

[61]

L. Liu, Z. Yao, Y. Deng, F. Gao, B. Liu, and L. Dong, “Morphology and Crystal-Plane Effects of Nanoscale Ceria on the Activity of CuO/CeO2 for NO Reduction by CO,” ChemCatChem 3 (2011): 978–989.

[62]

T. He, W. Wang, F. Shi, et al., “Mastering the Surface Strain of Platinum Catalysts for Efficient Electrocatalysis,” Nature 598 (2021): 76–81.

[63]

M. Daniel and S. Loridant, “Probing Reoxidation Sites by In Situ Raman Spectroscopy: Differences Between Reduced CeO2 and Pt/CeO2,” Journal of Raman Spectroscopy 43 (2012): 1312–1319.

[64]

W. Ouyang, F. Teng, J.-H. He, and X. Fang, “Enhancing the Photoelectric Performance of Photodetectors Based on Metal Oxide Semiconductors by Charge-Carrier Engineering,” Advanced Functional Materials 29 (2019): 1807672.

[65]

G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54 (1996): 11169–11186.

[66]

G. Mills, H. Jónsson, and G. K. Schenter, “Reversible Work Transition State Theory: Application to Dissociative Adsorption of Hydrogen,” Surface Science 324 (1995): 305–337.

[67]

H. J. Monkhorst and J. D. Pack, “Special Points for Brillouin-Zone Integrations,” Physical Review B 13 (1976): 5188–5192.

RIGHTS & PERMISSIONS

2025 The Author(s). Interdisciplinary Materials published by Wuhan University of Technology and John Wiley & Sons Australia, Ltd.

AI Summary AI Mindmap
PDF

80

Accesses

0

Citation

Detail

Sections
Recommended

AI思维导图

/