Synthesis and gas adsorption properties of nickel ferrite nanoparticles

HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY MASTER THESIS Synthesis and gas adsorption properties of nickel ferrite nanoparticles CAO XUAN TRUONG Truong.CX211148M@sis.hust.edu.vn Materials Science Supervisor: Assoc Prof Nguyen Van Quy Signature Dr Luong Ngoc Anh Signature Institute: International Training Institute for Materials Science HA NOI, 04/2023 SOCIALIST REPUBLIC OF VIETNAM Independence – Freedom – Happiness CONFIRMATION OF MASTER’S THESIS ADJUSTMENT Full name of the author : Cao Xuan Truong Thesis topic: Synthesis and gas adsorption properties of nickel ferrite nanoparticles Major: Material Science Student ID: 20211148M The author, the supervisor, and the Committee confirmed that the author has adjusted and implemented the thesis according to the report of the Committee on April 28th, 2023 with the following contents: - Literature review outline and content - Spelling and printing errors Day Supervisor Month Year Thesis’s author Assoc Prof Nguyen Van Quy Cao Xuan Truong COMMITTEE’S CHAIRMAN Prof Nguyen Phuc Duong THESIS TOPIC Synthesis and gas adsorption properties of nickel ferrite nanoparticles Supervisor Assoc Prof Nguyen Van Quy Acknowledgement First of all, I would like to express my greatest gratitude toward my supervisor, Assoc Prof Nguyen Van Quy for being an ideal teacher, mentor, and thesis supervisor, offering advice and encouragement with a perfect blend of insight and humor I also desire to extend my appreciation to Dr Luong Ngoc Anh, Dr Nguyen Thanh Vinh and Dr Tran Van Dang for their invaluable recommendations and explanations related to my research topic I would also like to express my special thanks to all lecturers and employees at ITIMs for creating a wonderful environment while I was on my course I also thank the project grant number B2021-BKA-04 Sincerely, I would like to thank my lab-mates at Room 202 for their strong support, endless assistance, regular encouragement and inspirations every single day Last but not least, my special gratitude is expressed to my dear family members, who are always by my side, both financial and mental supportive during my master program Abstract Industrialization and modernization in today society bring about many benefits Pollution caused by these processes put people’s health and environmental status at risk It is urgent that a sensor with high sensitivity, stable operation, low cost, low energy consumption and mobility is developed to monitor the pollution status and prevent potential risk A quartz crystal microbalance (QCM) sensor is researched to meet those requirements This sensor can detect a small concentration of gas by mass change principle To enhance the adsorption capabilities, metal oxides are deposited on the electrode of QCM sensor Among the most considerable sensing materials, NiFe2O4 nanoparticles with porous structure, large specific area and various functioning group on its surface can be considered suitable for being a good sensing layer of QCM sensor The material is fabricated by hydrothermal and co-precipitation methods The characterization of NiFe2O4 was investigated by some measuring methods Then the QCM sensors are coated and tested their gas sensing ability by QCM200 system After various experiments, it can be assured that a QCM coated NiFe2O4 sensor is capable of detecting SO2, NO2, H2S at room temperature In addition, the results suggest that the material are most responsive to SO2 and little deviated after a long time operating The mechanism of physisorption of nickel ferrites is also presented STUDENT Cao Xuan Truong TABLE OF CONTENTS INTRODUCTION 12 CHAPTER LITERATURE REVIEW 14 1.1 1.2 1.3 Introduction of nickel ferrite (NiFe2O4) 14 1.1.1 Overview of the structure of ferrites 14 1.1.2 Nickel Ferrite (NiFe2O4) 16 1.1.3 Fabrication methods 17 Introduction of quartz crystal microbalance (QCM) 18 1.2.1 Piezoelectric Effect 18 1.2.2 Quartz crystal microbalance 21 Quartz crystal microbalance gas sensor 24 1.3.1 Introduction of QCM gas sensor 24 1.3.2 QCM sensor working principle 25 CHAPTER EXPERIMENT DETAILS 28 2.1 2.2 2.3 Chemical and apparatus 28 2.1.1 Chemical 28 2.1.2 Apparatus 28 NiFe2O4 nanoparticles fabrication 28 2.2.1 NiFe2O4 nanoparticles fabrication by hydrothermal method 28 2.2.2 NiFe2O4 nanoparticles fabrication by co-precipitation method 29 Characterization methods 30 2.3.1 X-ray Diffraction (XRD) 30 2.3.2 Scanning Electron Microscope 30 2.3.3 Transmission electron microscope 31 2.3.4 Fourier Transform Infrared Spectroscopy (FTIR) 32 2.3.5 Surface area and pore size distribution measurements 33 2.4 Fabrication of NiFe2O4 sensing layer on the QCM electrode and gas sensing measurement 33 2.4.1 Fabrication of NiFe2O4 sensing layer on QCM 34 2.4.2 Gas sensing measurement 35 CHAPTER RESULTS AND DISCUSSION 37 3.1 Fabrication method investigation 37 3.1.1 Co-precipitation method 37 3.1.2 3.2 3.3 Hydrothermal method 38 Characterization 39 3.2.1 X-ray Diffraction 39 3.2.2 SEM images 40 3.2.3 Fourier transform Infrared Spectra 40 3.2.4 BET and BJH analysis 42 Gas sensing properties of QCM coated NiFe2O4 NPs 43 3.3.1 Mass density of NiFe2O4 NPs deposited on the electrode 43 3.3.2 Inorganic toxic gases adsorption ability 43 3.3.3 Long-term stability 49 3.3.4 Response and recover time 50 3.3.5 Selectivity 52 CONCLUSIONS 54 LIST OF PUBLICATION 62 ABBREVIATIONS BET Brunauer – Emmett – Teller BJH Barrett – Joyner – Halenda BVD Butterworth-Van Dyke DI Deionized water FTIR Fourier Transform Infrared Spectroscopy JCPDS Joint Committee on Powder Diffraction Standards ITIMS International Training Institute for Materials Science MFC Mass Flow Controller NFO NiFe2O4 NPs Nano particles ppm Parts per million QCM Quartz Crystal Microbalance sccm Standard cubic centimeters per minute SEM Scanning Electron Microscopy TEM Transmission Electron Microscope XRD X-ray Diffraction LIST OF FIGURES Figure 1.1 Schematic of a partial unit cell and ferrimagnetic ordering of spinel ferrite structure [44] 14 Figure 1.2 Cation distribution in spinel ferrites: (a) inverted ferrites, (b) manganese ferrites and (c) zinc manganese ferrites [18] 15 Figure 1.3 Atomic positions in the inverse spinel structure of NFO A portion of connecting (Fe,Ni)O6 octahedra around a FeO4 tetrahedron is also depicted, where “Oc” and “Te” in the suffix indicate the octahedron and tetrahedron 17 Figure 1.4 Typical device in hydrothermal method 18 Figure 1.5 The piezoelectric effect in the material: without piezoelectric polarization (A), the molecules subjected to an external force with charge forming (B), and piezoelectric effect on the surface Note that, P denotes polarization vector, F is applied external force [36] 19 Figure 1.6 Direct and inverse piezoelectric effect in the material 20 Figure 1.7 Practical application of the piezoelectric material [34] 20 Figure 1.8 The schematic of quartz crystal with electrode (a-b), the strain induced in an AT cut crystal on application of AC voltage (c), and the amplitude of vibration varies with the distance from the center of the sensor 22 Figure 1.9 The quartz crystal structure (A), AT-cut crystal (B), and crystal structure of -SiO2 (c) [44] 22 Figure 1.10 The Butterworth-Van Dyke (BVD) equivalent circuit for an unloaded quartz crystal microbalance, QCM under viscous and mass loading (A), and the device parameter versus frequency characteristic curve (B) [45] 23 Figure 1.11 The diagram of Quartz Crystal Microbalance oscillator 24 Figure 1.12 Crystal Holder components.[47] 24 Figure 1.13 (a) Schematic top view and cross-sectional view of QCM uncoated and coated with a sensing layer, and (b) the illustration of frequency decreasing due to active layer coating and during sensing measurements [50] 26 Figure 2.1 NiFe2O4 NPs hydrothermal method synthesis process 29 Figure 2.2 NiFe2O4 NPs co precipitation synthesis process 29 Figure 2.3 XRD measurement system in ITIMS 30 Figure 2.4 Working principle of scanning electron microscopy [60] 31 Figure 2.5 General layout of a TEM 32 Figure 2.6 (a) Schematic diagram of a Fourier transform infrared instrument (b) Michelson interferometer [64] 32 Figure 2.7 Spray coating system and spraying gun 35 Figure 2.8 Schematic diagram of gas measuring system 35 Figure 2.9 Gas measuring system 36 Figure 3.1 XRD spectra of NiFe2O4 at different annealing temperature (coprecipitation method) 37 Figure 3.2 TEM image of sample annealed at 600oC (left) and 800oC (right) 38 Figure 3.3 XRD spectra of NiFe2O4 at different annealing temperature (hydrothermal method) 38 Figure 3.4 XRD spectra of NiFe2O4 fabricated by co-precipitation (C - NFO) and hydrothermal method (H - NFO) 39 Figure 3.5 SEM image and size distribution figure of C - NFO sample 40 Figure 3.6 SEM image and size distribution figure of H - NFO sample 40 Figure 3.7 The Fourier transform infrared spectrum of C – NFO (a) and H – NFO (b) 41 Figure 3.8 Adsorption and desorption isotherm and pore size distribution of C NFO (a) and H - NFO (b) 42 Figure 3.9 Gas mass absorbed on the QCM-C - NFO and QCM-H – NFO 44 Figure 3.10 The relationships between the frequency shifts/adsorbed mass on the QCM C - NFO electrode and target gases concentrations from to 20 ppm of SO2, NO2 46 Figure 3.11 The relationships between the frequency shifts/adsorbed mass on the QCM H - NFO electrode and target gases concentrations from to 20 ppm of SO2, NO2 46 Figure 3.12 Linear dependence of the sensitivity factor on the SO2, NO2 concentrations between 5ppm and 20ppm of two sensors 47 Figure 3.13 The comparison between SO2 and NO2 sensibility of both sensors 48 Figure 3.14 The long-term stability of gas adsorption performance 49 Figure 3.15 The response and recover time of C – NFO coated sensor at different concentration of SO2 (a) and NO2 (b) 50 Figure 3.16 The response and recover time of H – NFO coated sensor at different concentration of SO2 (a) and NO2 (b) 51 Figure 3.17 Response towards different gases in different concentrations of C NFO sample 52 Figure 3.18 Response towards different gases in different concentrations of H NFO sample 53 10 Table 3.5 Summarized information of QCM – H – NFO Con (ppm) 10 15 20 0.01943 0.0424 0.06184 0.08304 Δf (Hz) 1.1 2.4 3.5 4.7 S (‰) 0.1463 0.319 0.465 0.625 Δm (µg cm-2) 0.0159 0.0424 0.06007 0.07951 Δf (Hz) 0.9 2.4 3.4 4.5 S (‰) 0.1197 0.319 0.439 0.5722 Δm (µg cm-2) SO2 NO2 Figure 3.13 The comparison between SO2 and NO2 sensibility of both sensors 48 3.3.3 Long-term stability Not only is the response important to a gas sensor, but also the stability of it when operating in a long period of time Figure 3.9 has shown the periodic stability of the sensors so in this section, long term stability is investigated Both sensors are weekly recorded in a month to collect the results After weeks, there are no significant changes in the ability of adsorption of the material QCM – C - NFO exhibit a stability with SO2 According to the figure, the adsorption performance of C - NFO NPs sensor slightly fluctuate around 0.0538, 0.1603 and 0.2850 µg.cm-2 for 5, 10, 15 ppm Compared with the first experiment time, the mean data are only deviated 2.16% The same situation happened when recording the NO2 adsorption data of H - NFO sample The deviation is only 7,9% Figure 3.14 The long-term stability of gas adsorption performance 49 3.3.4 Response and recover time The response time of the sensor can be determined when the resonance frequency reached 90% of the maximum frequency shift in a measuring period In contrast, the recovery time is the moment the sensor recovers 90% of the maximum frequency shift (a) (b) Figure 3.15 The response and recover time of C – NFO coated sensor at different concentration of SO2 (a) and NO2 (b) 50 (a) (b) Figure 3.16 The response and recover time of H – NFO coated sensor at different concentration of SO2 (a) and NO2 (b) At the same reaction period, the response and recover time vary at different concentrations and different kinds of target gases However, the time that sensors need to reach 90% of the maximum frequency shift of SO2 is slightly shorter than that of NO2 in both sensors The same thing happens to the recovery time Meanwhile, H – NFO coated sensor responses and recovers faster than C – NFO coated sensor Compared to some sensing material, NiFe2O4 NPs show a better result, which detailed in the following table 51 Table 3.6 Comparison of SO2 response and recover time of different sensing material at the same concentrations Sensing material Con (ppm) tres/ trec (s) Reference MW-CNTs 15 100/90 [52] GO-NSs 15 80/100 [9] Fe3O4/αFeOOH nanorod 15 55/75 [77] NiFe2O4 NPs 15 58/61* This study * the best result in this investigation 3.3.5 Selectivity Figure 3.17 Response towards different gases in different concentrations of C - NFO sample 52 Figure 3.18 Response towards different gases in different concentrations of H - NFO sample Apart from SO2 and NO2 presented in the previous section, other inorganic gases are investigated However, the QCM coated NiF2O4 sensors don’t respond well with these gases S – factor is used to defined the frequency shift per unit of gas concentration injected in the measuring chamber In general, S – factor mainly increase while increasing the gas concentration With the highest concentration, the S – factors are determined at 0.4, 0.34, and 0.19 (Hz/ppm) for SO2, NO2, H2S respectively The same experiment was carried out with QCM – H - NFO sensor The recorded results are 0.235, 0.225 and 0.0037 (Hz/ppm) for SO2, NO2, NH3 Thus, NiFe2O4 NPs are more sensitive with SO2 than some reference inorganic toxic gas in room temperature The SO2, NO2 and H2S molecules are adsorbed by NiFe2O4 NPs through the following mechanisms • The hydrogens bond between H atom of O-H active groups (as show in FT-IR spectra) and O/S atoms of (SO2, NO2)/H2S [77] • The interaction of five semi-saturation 4D-orbitals of Fe3+ ion with a lone pair electron of S atom in SO2 molecular via like-hydrogens bond [78][72] • The H2S and SO2 adsorption capacity of the Ni-O bond (a theoretical study), in which H2S has stronger adsorption reaction than SO2 [79] From the data, it can be assumed that QCM coated NiFe2O4 sensors are able to respond to SO2 better than NO2, H2S and NH3, which demonstrates that the molecular weight and pole-pole interaction of target gases strongly effect on the gas adsorption performance of the QCM sensor using NiFe2O4 NPs 53 CONCLUSIONS Based on the results and analysis presented above, there are some conclusions can be drawn: ✓ Successfully fabricate the NiFe2O4 NPs by co-precipitation method and hydrothermal method The as-synthesized materials have great uniformity, high purity, small size (~20nm in diameter), large specific area and pore size (SBET = 69.37 and 86.59 m2/g, Dpore = 8.2 and 11.4 nm of C – NFO and H – NFO respectively), which is suitable for being the adsorption layer of mass changing sensor type ✓ Successfully synthesize the QCM coated NiFe2O4 with different mass density 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