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用于亚ppm级氢气检测的金属氧化物固溶体设计

Design of a Metal-Oxide Solid Solution for Sub-ppm H Detection.

作者信息

Spagnoli Elena, Gaiardo Andrea, Fabbri Barbara, Valt Matteo, Krik Soufiane, Ardit Matteo, Cruciani Giuseppe, Della Ciana Michele, Vanzetti Lia, Vola Gabriele, Gherardi Sandro, Bellutti Pierluigi, Malagù Cesare, Guidi Vincenzo

机构信息

Department of Physics and Earth Sciences, University of Ferrara, via Giuseppe Saragat 1, Ferrara 44122, Italy.

MNF-Micro Nano Facility Sensors and Devices Center, Bruno Kessler Foundation, via Sommarive 18, Trento 38123, Italy.

出版信息

ACS Sens. 2022 Feb 25;7(2):573-583. doi: 10.1021/acssensors.1c02481. Epub 2022 Feb 16.

Abstract

Hydrogen is largely adopted in industrial processes and is one of the leading options for storing renewable energy. Due to its high explosivity, detection of H has become essential for safety in industries, storage, and transportation. This work aims to design a sensing film for high-sensitivity H detection. Chemoresistive gas sensors have extensively been studied for H monitoring due to their good sensitivity and low cost. However, further research and development are still needed for a reliable H detection at sub-ppm concentrations. Metal-oxide solid solutions represent a valuable approach for tuning the sensing properties by modifying their composition, morphology, and structure. The work started from a solid solution of Sn and Ti oxides, which is known to exhibit high sensitivity toward H. Such a solid solution was empowered by the addition of Nb, which─according to earlier studies on titania films─was expected to inhibit grain growth at high temperatures, to reduce the film resistance and to impact the sensor selectivity and sensitivity. Powders were synthesized through the sol-gel technique by keeping the Sn-Ti ratio constant at the optimal value for H detection with different Nb concentrations (1.5-5 atom %). Such solid solutions were thermally treated at 650 and 850 °C. The sensor based on the solid solution calcined at 650 °C and with the lowest content of Nb exhibited an extremely high sensitivity toward H, paving the way for H ppb detection. For comparison, the response to 50 ppm of H was increased 6 times vs SnO and twice that of (Sn,Ti)O.

摘要

氢气在工业过程中被广泛采用,是存储可再生能源的主要选择之一。由于其高爆炸性,氢气检测对于工业、储存和运输中的安全至关重要。这项工作旨在设计一种用于高灵敏度氢气检测的传感膜。由于其良好的灵敏度和低成本,化学电阻式气体传感器已被广泛研究用于氢气监测。然而,在亚ppm浓度下进行可靠的氢气检测仍需要进一步的研究和开发。金属氧化物固溶体是一种通过改变其组成、形态和结构来调节传感性能的有价值的方法。这项工作从锡和钛的氧化物固溶体开始,已知该固溶体对氢气表现出高灵敏度。通过添加铌增强了这种固溶体,根据早期对二氧化钛薄膜的研究,铌有望抑制高温下的晶粒生长,降低薄膜电阻,并影响传感器的选择性和灵敏度。通过溶胶-凝胶技术合成了粉末,保持锡-钛比例恒定在氢气检测的最佳值,并添加不同浓度(1.5-5原子%)的铌。这些固溶体在650和850℃下进行了热处理。基于在650℃煅烧且铌含量最低的固溶体制备的传感器对氢气表现出极高的灵敏度,为氢气ppb检测铺平了道路。相比之下,对50 ppm氢气的响应比SnO增加了6倍,是(Sn,Ti)O的两倍。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/38ed/8886563/d565e7420886/se1c02481_0002.jpg

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