Perception-transduction-transmission separation bionic H₂S sensor

Abstract

Achieving high selectivity, high sensitivity, and superior conductivity simultaneously for chemiresistive gas sensors (CGS) remains a significant challenge due to inherent trade-offs among the material's properties. Inspired by biological olfaction, we design and fabricate a Ni-MOF/SnO₂ heterojunction as a perception-transduction-transmission separation membrane for bionic CGS, where Ni-MOF acts as a selective perception layer for H₂S, SnO₂ serves as the electron transmission and proton blocking layer, while the heterojunction enables efficient signal transduction from perception to transmission. The sensor demonstrates exceptional performance, including fingerprint-level selectivity, high moisture stability, and an ultra-low detection limit of 10 ppb. Notably, the sensor operates based on the heterojunction rectification enhancement model. The sensitivity is solely determined by the Ni-MOF perception layer, while the baseline current is governed by the SnO₂ transmission layer. By reducing the resistance of SnO₂, the net response is geometrically amplified. Additionally, applying a bias voltage enables geometric acceleration of the response/recovery rates. This study proposes a novel strategy for designing high-performance CGS.

Keywords

chemiresistive gas sensor / H₂S / heterojunction rectification enhancement / Ni-MOF / perception-transduction-transmission separation

References

[1] Bostelaar T, Vitvitsky V, Kumutima J, et al. Hydrogen sulfide oxidation by myoglobin. J Am Chem Soc. 2016;138(27):8476-8488.

[2] Wang C, Chen Z, Chan CLJ, et al. Biomimetic olfactory chips based on large-scale monolithically integrated nanotube sensor arrays. Nat Electron. 2024;7(2):157-167.

[3] Seiyama T, Kato A, Fujiishi K, Nagatani M. A new detector for gaseous components using semiconductive thin films. Anal Chem. 1962;34(11):1502-1503.

[4] Korotcenkov G, Cho BK. Metal oxide composites in conductometric gas sensors: achievements and challenges. Sens Actuators, B. 2017;244:182-210.

[5] Xue Z, Yan M, Yu X, et al. One-dimensional segregated single Au sites on step-rich ZnO ladder for ultrasensitive NO₂ sensors. Chem. 2020;6(12):3364-3373.

[6] Tan K, Zuluaga S, Wang H, et al. Interaction of acid gases SO₂ and NO₂ with coordinatively unsaturated metal organic frameworks: M-MOF-74 (M = Zn, Mg, Ni, Co). Chem Mater. 2017;29(10):4227-4235.

[7] Liu Q, Huang R, Tang J, Zhang H, Liu M, Fang Y. A nanofilm-based fluorescent sensor toward highly efficient detection of ethephon. Anal Chem. 2024;96(6):2559-2566.

[8] Koo W-T, Jang J-S, Kim I-D. Metal-organic frameworks for chemiresistive sensors. Chem. 2019;5(8):1938-1963.

[9] Li L, Zhang S, Lu Y, et al. Highly selective and sensitive detection of volatile sulfur compounds by ionically conductive metal-organic frameworks. Adv Mater. 2021;33(52):2104120.

[10] Small LJ, Henkelis SE, Rademacher DX, et al. Near-zero power MOF-based sensors for NO₂ detection. Adv Funct Mater. 2020;30(50):2006598.

[11] Wu X, Tian X, Zhang W, et al. Solution-processable MOF-on-MOF system constructed via template-assisted growth for ultratrace H₂S detection. Angew Chem Int Ed. 2024;63(49):e202410411.

[12] Campbell MG, Liu SF, Swager TM, Dincă M. Chemiresistive sensor arrays from conductive 2D metal–organic frameworks. J Am Chem Soc. 2015;137(43):13780-13783.

[13] Singh E, Meyyappan M, Nalwa HS. Flexible graphene-based wearable gas and chemical sensors. ACS Appl Mater Interfaces. 2017;9(40):34544-34586.

[14] Kumar S, Mirzaei A, Kumar A, et al. Nanoparticles anchored strategy to develop 2D MoS₂ and MoSe₂ based room temperature chemiresistive gas sensors. Coord Chem Rev. 2024;503:215657.

[15] Billesbølle CB, de March CA, van der Velden WJC, et al. Structural basis of odorant recognition by a human odorant receptor. Nature. 2023;615(7953):742-749.

[16] Efros AL, Delehanty JB, Huston AL, Medintz IL, Barbic M, Harris TD. Evaluating the potential of using quantum dots for monitoring electrical signals in neurons. Nat Nanotechnol. 2018;13(4):278-288.

[17] Carton A, Mesbah A, Mazet T, Porcher F, François M. Ab initio crystal structure of nickel (II) hydroxy-terephthalate by synchrotron powder diffraction and magnetic study. Solid State Sci. 2007;9(6):465-471.

[18] Yan Y, Gu P, Zheng S, Zheng M, Pang H, Xue H. Facile synthesis of an accordion-like Ni-MOF superstructure for high-performance flexible supercapacitors. J Mater Chem A. 2016;4(48):19078-19085.

[19] Zhao S, Wang Y, Dong J, et al. Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat Energy. 2016;1(12):16184.

[20] Rodríguez-Maciá P, Reijerse EJ, van Gastel M, et al. Sulfide protects [FeFe] hydrogenases from O₂. J Am Chem Soc. 2018;140(30):9346-9350.

[21] Shafaat HS, Yang JY. Uniting biological and chemical strategies for selective CO₂ reduction. Nat Catal. 2021;4(11):928-933.

[22] Felbek C, Arrigoni F, de Sancho D, et al. Mechanism of hydrogen sulfide-dependent inhibition of FeFe hydrogenase. ACS Catal. 2021;11(24):15162-15176.

[23] Vincent KA, Belsey NA, Lubitz W, Armstrong FA. Rapid and reversible reactions of [NiFe]-hydrogenases with sulfide. J Am Chem Soc. 2006;128(23):7448-7449.

[24] Hamon L, Serre C, Devic T, et al. Comparative study of hydrogen sulfide adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal−organic frameworks at room temperature. J Am Chem Soc. 2009;131(25):8775-8777.

[25] Yang J, Xiong P, Zheng C, Qiu H, Wei M. Metal–organic frameworks: a new promising class of materials for a high performance supercapacitor electrode. J Mater Chem A. 2014;2(39):16640-16644.

[26] Zhu B, Wang B, Wang Y, et al. Charge separation and transport in La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ and ion-doping ceria heterostructure material for new generation fuel cell. Nano Energy. 2017;37:195-202.

[27] Wang S, Yan M, Li Y, Vinado C, Yang J. Separating electronic and ionic conductivity in mix-conducting layered lithium transition-metal oxides. J Power Sources. 2018;393:75-82.

[28] Ponomareva VG, Kovalenko KA, Chupakhin AP, Dybtsev DN, Shutova ES, Fedin VP. Imparting high proton conductivity to a metal–organic framework material by controlled acid impregnation. J Am Chem Soc. 2012;134(38):15640-15643.

[29] George KH, Shimizu JMT, Kim SR. Proton conduction with metal-organic frameworks. Science. 2013;341(6144):354-355.

[30] Hai G, Tao Z, Gao H, et al. Targeted synthesis of covalently linked Ni-MOFs nanosheets/graphene for oxygen evolution reaction by computational screening of anchoring primers. Nano Energy. 2021;79:105418.

[31] Wang Y, Song Y, Xia Y. Electrochemical capacitors: mechanism, materials, systems, characterization and applications. Chem Soc Rev. 2016;45(21):5925-5950.

[32] Yang Y, Zhang P, Hao L, Cheng P, Chen Y, Zhang Z. Grotthuss proton-conductive covalent organic frameworks for efficient proton pseudocapacitors. Angew Chem Int Ed Engl. 2021;60(40):21838-21845.

[33] Trakhtenberg LI, Gerasimov GN, Gromov VF, Belysheva TV, Ilegbusi OJ. Effect of composition on sensing properties of SnO₂+In₂O₃ mixed nanostructured films. Sens Actuators, B. 2012;169:32-38.

[34] Liu B, Luo Y, Li K, Wang H, Gao L, Duan G. Room-temperature NO₂ gas sensing with ultra-sensitivity activated by ultraviolet light based on SnO₂ monolayer array film. Adv Mater Interfaces. 2019;6(12):1900376.

[35] Correa-Baena J-P, Artyushkova K, Santoro C, Atanassov P, Agrios AG. Morphological characterization of ALD and doping effects on mesoporous SnO₂ aerogels by XPS and quantitative SEM image analysis. ACS Appl Mater Interfaces. 2016;8(15):9849-9854.

[36] Li Y, Wu X, Zuo G, et al. An n-n heterojunction configuration for efficient electron transport in organic photovoltaic devices. Adv Funct Mater. 2023;33(9):2209728.

[37] Xu Z, Luo Y, Duan G. Self-assembly of Cu₂O monolayer colloidal particle film allows the fabrication of CuO sensor with superselectivity for hydrogen sulfide. ACS Appl Mater Interfaces. 2019;11(8):8164-8174.

[38] Chernikova V, Yassine O, Shekhah O, Eddaoudi M, Salama Khaled N. Highly sensitive and selective SO₂ MOF sensor: the integration of MFM-300 MOF as a sensitive layer on a capacitive interdigitated electrode. J Mater Chem A. 2018;6(14):5550-5554.

[39] Hou C, Tai G, Liu Y, Liu X. Borophene gas sensor. Nano Res. 2022;15(3):2537-2544.

[40] Fowler JD, Allen MJ, Tung VC, Yang Y, Kaner RB, Weiller BH. Practical chemical sensors from chemically derived graphene. ACS Nano. 2009;3(2):301-306.

[41] Lipatov A, Varezhnikov A, Wilson P, Sysoev V, Kolmakov A, Sinitskii A. Highly selective gas sensor arrays based on thermally reduced graphene oxide. Nanoscale. 2013;5(12):5426-5434.

[42] Campbell MG, Sheberla D, Liu SF, Swager TM, Dincă M. Cu₃(hexaiminotriphenylene)₂: an electrically conductive 2D metal–organic framework for chemiresistive sensing. Angew Chem Int Ed. 2015;54(14):4349-4352.

[43] Pham T, Li G, Bekyarova E, Itkis ME, Mulchandani A. MoS₂-based optoelectronic gas sensor with sub-parts-per-billion limit of NO₂ gas detection. ACS Nano. 2019;13(3):3196-3205.

[44] Kim H, Jin C, Park S, Kim S, Lee C. H₂S gas sensing properties of bare and Pd-functionalized CuO nanorods. Sens Actuators, B. 2012;161(1):594-599.

[45] Hsu K-C, Fang T-H, Hsiao Y-J, Li Z-J. Rapid detection of low concentrations of H₂S using CuO-doped ZnO nanofibers. J Alloys Compd. 2021;852:157014.

[46] Chen L, Li J, Wang Y, Feng H, Yan D, Gu X. High-densities of free holes in homoepitaxial n-GaN induced by fluorine-plasma ion implantation. Solid State Electron. 2022;189:108226.

[47] Yang C, Liu Z, Su Z, et al. Combined effect of oxygen vacancies and mesopore sizes in ZnO/SiO₂ adsorbents on boosting the H₂S removal efficiency in moist conditions. Adv Funct Mater. 2024;34(49):2409214.

[48] Zhang S, Yao Y, Jiao X, et al. Mo₂N–W₂N heterostructures embedded in spherical carbon superstructure as highly efficient polysulfide electrocatalysts for stable room-temperature Na–S batteries. Adv Mater. 2021;33(43):2103846.

[49] Wu S-C, Huang Y-H, Liao C-R, et al. Rational design of a polysulfide catholyte electrocatalyst by interfacial engineering based on novel MoS₂/MoN heterostructures for superior room-temperature Na–S batteries. Nano Energy. 2021;90:106590.

[50] Obeso JL, Amaro DR, Flores CV, et al. Chemical transformations of highly toxic H₂S to promising clean energy in MOFs. Coord Chem Rev. 2023;485:215135.

[51] Calow JT, Deasley PJ, Owen SJT, Webb PW. A review of semiconductor heterojunctions. J Mater Sci. 1967;2(1):88-96.

[52] Sze SM, Ng KK. p-n Junctions. Physics of Semiconductor Devices. John Wiley & Sons, Inc; 2006:77-133.

[53] Wang J, Song Y, Hu J, et al. Photocatalytic hydrogen evolution on P-type tetragonal zircon BiVO₄. Appl Catal, B. 2019;251: 94-101.

[54] Grätzel M. Photoelectrochemical cells. Nature. 2001;414(6861):338-344.

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