The Design, Simulation, and Construction of an O2, C3H8, and CO2 Gas Detection System Based on the Electrical Response of MgSb2O6 Oxide
Round 1
Reviewer 1 Report
Comments and Suggestions for Authors1. I suggest using the references more accurately, for example, instead of [2,3] or [4,5] etc. to refer to each source separately and in detail.
2. The Introduction section is clearly too short; I recommend expanding it. The state-of-the-art is also not sufficiently described.
3. The number of references is also not sufficient.
4. I am wondering if it makes sense to restructure the paper and clearly distinguish section “Materials and Methods”.
5. The prototype is capable of detecting one, two, or three different gases depending on the proposed configuration. Did you check cross-sensitivity to other gases?
6. Line 379, 392. Check other misprints in the text.
Author Response
- I suggest using the references more accurately, for example, instead of [2,3] or [4,5] etc. to refer to each source separately and in detail.
Response: We appreciated the reviewer’s suggestion in this point. In the improved version of our paper, the cites were placed in the adequate places and separated according to the suggestion.
- The Introduction section is clearly too short; I recommend expanding it. The state-of-the-art is also not sufficiently described.
Response: Dear reviewer, we appreciate your observation to improve the quality of our work. In the Introduction of the manuscript, new information was incorporated in concordance to your suggestions. Additionally, new cites were placed to strengthen our response in this part. The new information placed in the introduction is as follows:
- In the paragraph 1 the following as added:
In the fabrication of semiconductive binary oxides [4],[5], ternary perovskite oxides [6], spinel oxides [7] and trirutile semiconductive oxides have been employed. Particularly, the triturile semiconductive oxides, such as: ZnSb2O6, MnSb2O6 and NiSb2O6 [8], [9], [10], [11], [12], [13], [14], [15] are very attractive materials given their performance in catalytic activity, thermic stability, good capacity and efficiency for toxic environments such as the one where the CO, CO2, C3H8 and GLP gases are prevalent [16]. Based on the results reported in the literature, these gas detection properties are due to the different particle morphologies and variable sizes which can reach up to 100 nm [17]. In reference [18], the author mentions, reducing the particle size (to nanometric scale), the adsorption and desorption of oxygen species ( ) on the compound surface substantially increases due to the temperature, causing an incrementation in the sensibility and dynamic response [17]. With the improvement of these parameters in the detection of gases deploying trirutile materials, the design and construction of new toxic gas detecting devices operating in high temperatures and concentrations is favored [19], making it possible to develop efficient industrial protection systems.
- In paragraph 2 the following was added:
On the other hand, for the gas sensors, the adaptation of their electrical signals is typically achieved through programmable devices [20] and analog electronics [21]. In the design of digital protection systems, it is important to take in consideration: the signal adaptation between the sensor and the microcontroller, the electric response of the sensor, the resolution of the analog-to-digital convertor in the analogic input port of the microcontroller, the machine time, the bit architecture, oscillator frequency and the connectivity to other devices [22]. Meanwhile, in the design of analog protection systems, it is taken in consideration the electric response of the sensor, the analog circuit type, the electronic components response times and the cascade connection of the circuits [23]. Digital protection systems have the advantage of connectivity with other equipment and their design can be modified through programming, nonetheless, the analog devices have limited design applications and they have the disadvantage of having no connectivity with other devices. Taking this in consideration, the development of programmable protection systems is desirable given their connectivity with the emerging technologies.
- The number of references is also not sufficient.
Response: This is a very adequate recommendation to strengthen our research. Furthermore, we agree with the reviewer’s suggestion. In the updated version of our paper, new up-to-date bibliographic reference were added referring to the field of semiconductive oxides researched as gas sensors. Subsequently, some of the integrated references are mentioned in the following list.
- Fan-Jian Meng, Rui-Feng Xin, Shan-Xin Li. Metal Oxide Heterostructures for Improving Gas Sensing Properties: A Review. Materials 2023, 16, 263. https://doi.org/10.3390/ma16010263
- Guangyao Li, Xitong Zhu, Junlong Liu, Shuyang Li and Xiaolong Liu. Metal Oxide Semiconductor Gas Sensors for Lung Cancer Diagnosis. Chemosensors 2023, 11, 251. https://doi.org/10.3390/chemosensors11040251
- Juan Casanova-Chafer, Rocio Garcia-Aboal, Pedro Atienzar, Carla Bittencourt, Eduard Llobet. Perovskite@Graphene Nanohybrids for Breath Analysis: A Proof-of-Concept. Chemosensors 2021, 9, 215. https://doi.org/10.3390/chemosensors9080215
- Zivar Azmoodeh, Hossain Milani Moghaddam Shahruz Nasirian. Hydrogen gas sensing feature of polypyrrole nanofibers assisted by spinel ZnMn2O4 microspheres in dynamic conditions. International Journal of Hydrogen Energy, 47 (2022) 29971-29984
- Singh, S.; Singh, A.; Singh, A.; Tandon, P. A stable and highly sensitive room-temperature liquefied petroleum gas sensor based on nanocubes/cuboids of zinc antimonate. RSC Adv. 2020, 10, 20349–20357
- Archana Singh, Ajendra Singh, Satyendra Singh, Poonam Tandon. Nickel antimony oxide (NiSb2O6): A fascinating nanostructured material for gas sensing application, Chemical Physics Letters 2016, 646, 41-46
- Zhang L.; Li F.; Yang Y.; Li D.; Yu H.; Dong X., Polyoxometalates/Metal-organic frameworks-derived ZnO/ZnWO4 nanoparticles for highly sensitive selective ppb-level NO2 Chemical Engineering Journal, 2024, Vol. 499, 156604.
- Li P.; Yang Y.; Li F.; Pei W.; Li D.; Yu H.; Dong X.; Wang D., Effect of Polyoxometalates electron acceptor decoration on NO2 sensing behavior of ZnS microspheres toward rapid and ultrahigh response. Sensors and Actuators B: Chemical, 2025, Vol. 425, 137111.
- Zhang L.; Wang T.; Yang Y.; Wei M.; Li F.; Yu H.; Dong X., In situ synthesis of polyoxometalate-derved MoS2/phosphomolybdic acid composites for highly sensitive NO2 Journal of alloys and compounds, 2024, Vol 977, 173430.
- Zhang L.; Tian J.; Wang Y.; Wang T.; Wei M.; Li F.; Li Y.; Yang Y.; Yu H.; Dong X., Polyoxometelates electron acceptor-intercalated In2O3@SnO2 nanofibers for chemiresistive ethanol gas sensors. Sensors and Actuators B: Chemical, 2024, Vol 410, 135728.
- Zhang M.; Yang Y.; Li D.; Yu H.; Dong X.; Wang T., First Polyoxometalate-modified SnS2 composite nanostructurate gas sensor toward enhanced sensitivity and high selectivity NO2 Sensors and Actuators B: Chemical, 2024, Vol. 409, 135641.
- Song P. and Wang T., Application of polyoxometelates in chemiresistive gas sensors: A Review. ACS sensors, 2022, Vol 7, Issue 12, pp 3634-3643.
- Matvei Andreev, Maxim Topchiy, Andrey Asachenko, Artemii Beltiukov, Vladimir Amelichev, Alina Sagitova, Sergey Maksimov, Andrei Smirnov, Marina Rumyantseva, Valeriy Krivetskiy. Electrical and Gas Sensor Properties of Nb(V) Doped Nanocrystalline β-Ga2O3. Materials 2022, 15, 8916. https://doi.org/10.3390/ma15248916
- Singh, S.; Singh, A.; Singh, A.; Rathore, S.; Yadav, B.C.; Tandon, P. Nanostructured cobalt antimonate: a fast responsive and highly stable sensing material for liquefied petroleum gas detection at room temperature. RSC Adv. 2020, 10, 33770–33781.
- Jorge Alberto Ramírez-Ortega, Héctor Guillén-Bonilla, Alex Guillén-Bonilla, Verónica María Rodríguez-Betancourtt, A. Sánchez-Martínez, José Trinidad Guillén-Bonilla, Lorenzo Gildo-Ortiz, Emilio Huízar-Padilla, Juan Reyes-Gómez. Synthesis of the oxide NiSb2O6 and its electrical characterization in toxic atmospheres for its application as a gas sensor. J Mater Sci: Mater Electron (2022) 33:18268–18283.
- Jorge Alberto Ramírez-Ortega, José Trinidad Guillén-Bonilla, Alex Guillén-Bonilla, Verónica María Rodríguez-Betancourtt, Lorenzo Gildo-Ortiz, Oscar Blanco-Alonso, Víctor Manuel Soto-García, Maricela Jiménez-Rodríguez. Héctor Guillén-Bonilla. Preparation of Powders Containing Sb, Ni, and O for the Design of a Novel CO and C3H8 Appl. Sci. 2021, 11, 9536. https://doi.org/10.3390/app11209536
- Guillen Bonilla J. ; Guillen Bonilla A.; Casillas Zamora A.; and Guillen Bonilla H., Zinc aluminate (ZnAl2O4) applied in the development of a propane gas sensor and in the design of a digital gas detector. J Mater Sci: Mater Electron, 2023 34:967
- Ramírez-Ortega J. A.; Guillén-Bonilla J. T.; Guillén-Bonilla A.; Rodríguez Betancourtt V. M.; Gildo Ortiz L.; Blanco Alonso O.; Soto-García V. M.; Jiménez Rodríguez M; Guillén Bonilla H., Preparation of Powders Containing Sb, Ni, and O for the Design of a Novel CO and C3H8 Sensor. Sci. 2021, 11, 9536. https://doi.org/10.3390/app11209536
- Quintana Barcia, P. J., & García, J. (2023). Signal conditioning I: adaptation and protection stages. En Encyclopedia of Electrical and Electronic Power Engineering(pp. 46-56). https://doi.org/10.1016/B978-0-12-821204-2.00058-1
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- Proakis J. G.; Manolakis D. G., Digital signal processing, principles, algorithms and applications. Prentice-Hall International, 2017, Fourth Edition
- Stergiopoulos S., Advances signal processing. CRC press, 2017, 2nd Edition, https://doi.org/10.4324/9781315219042
- I am wondering if it makes sense to restructure the paper and clearly distinguish section “Materials and Methods”.
Response: Dear reviewer, we appreciated your commentary to enhance the quality of our work. Taking in consideration the valuable recommendation, the improved version of our paper was restructured and divided in sections and subsections. Henceforth, the paper has the following structure: 1. Introduction, 2. Methods, 3. Results, 4. Discussion and 5. Conclusions (along with their respective subsections). In the Introduction, a background describing the necessary requirements to build a gas detection device and a brief review about our research in the paper Technologies-3443382 is provided. In the Methods section, the methodology of our work is described. In the Results section, the experimental MgSb2O6 oxide characterization results are presented. Based in the material’s electric response, an electronic circuit is proposed and analyzed in every section, obtaining the design of a propane gas detector device. In base to the analysis, the device is simulated and built, obtaining a propane gas detector prototype. In the Discussion section, the most relevant aspects of our work are mentioned, discussed and analyzed. Lastly, in the last section Conclusions, the most relevant conclusions are mentioned.
- The prototype is capable of detecting one, two, or three different gases depending on the proposed configuration. Did you check cross-sensitivity to other gases?
Response: This is a very good question. In the improved version of our manuscript, new percentage of sensibility results in functions to the gases were incorporated (see Figure 5), located in section 3.3 Gas sensing properties analysis. To strengthen our answer to this question, an ample explanation of the obtained sensibility results is provided in the proposed condition exposed in the experimental methods section (2.3 Gas measurement tests)
- Line 379, 392. Check other misprints in the text.
Response: We are grateful to point out the mistakes found in our paper. The updated document was corrected in concordance.
Author Response File: Author Response.docx
Reviewer 2 Report
Comments and Suggestions for AuthorsThis paper presents the design, simulation, and assembly of a novel gas detection device. The prototype is capable of detecting O2, C3H8, CO2. The gas detector developed in this study is capable of operating at high temperatures and handling high gas concentrations, making it ideal for industries that require combustion processes. However, there are still some unresolved issues in the manuscript, which necessitates further revisions. The following are comments on the manuscript:
1. In the Abstract, author should provide some main data of this work.
2. In the Introduction, line 47-49, some related literatures about gas sensing semiconductors should be cited to enhance the importance and readability.
3. Some basic characterizations of MgSb2O6 should be measured, such as SEM and XRD.
4. Why did the author choose 400°C as the operating temperature? How about the sensing performances at higher or lower temperature?
5. How about the influences of relative humidity
Author Response
- In the Abstract, author should provide some main data of this work.
Response: We agree with the reviewer’s recommendation. In a section of our improved manuscript, new information about the microstructural characteristics and crystallography of our MgSb2O6 sensors were added. Furthermore, a data summary of the Dynamic responses of our material and the resistance changes during the selectivity experiments in the O2, C3H8, CO2 gases was placed. This information was incorporated in the Abstract of our paper as suggested by the reviewer.
- In the Introduction, line 47-49, some related literatures about gas sensing semiconductors should be cited to enhance the importance and readability.
Response: We agree with the reviewer regarding the importance of incorporation up-to-date citations. Our paper was updated and improved with further information in the introduction of our work, considering the references proposed by the reviewer. Additionally, the introduction was enhanced by adding more detailed descriptions of the properties and characteristics of the semiconductive oxides that have been reported as potential gas sensors. All of this information was based in an extensive literature review regarding the application of semiconductors as gas sensors. The cites proposed by the reviewer and those found in the literature were included and can be consulted in the list of references in this paper (cites 4 to 58).
- Some basic characterizations of MgSb2O6 should be measured, such as SEM and XRD.
Response: This is a good commentary and observation from part of the reviewer. In the improved manuscript, the new microstructure characterization (SEM) and crystalline (XRD) were performed from our MgSb2O6 powders of calcinated at 700 °C. For them, a x-ray diffraction study was done beforehand from the powders obtained after the material synthesis calcinated at 700 °C (see section 3.1 XRD analysis). According to these results (see Figure 2), the peaks of the diffractogram obtained from the compound were indexed and compared with those of the database in PDF No. 88-1725, finding that the oxide presents the cell parameters of a = 4.64 Å and c = 9.25 Å, with a spatial group of P42/mnm. Furthermore, according to the database file, the compound belongs to the material family of the trirutile types. The results of the XRD were compared with those found in other studies in the literature and we found consistency with what the authors reported in their papers concerning the same compound and following other synthesis methods. On the other hand, the peaks of the diffractogram of Figure 2 were taken in consideration to determine the crystal size of MgSb2O6. For this calculation, the Scherrer’s equation reported in reference [29] was employed. The description and discussion of these results were incorporated in detail in section 3.1 XRD analysis.
[29] Gildo-Ortiz, L.; Rodríguez-Betancourtt, V.-M.; Ramírez Ortega, J.A.; Blanco-Alonso, O. An Alternative Approach for the Synthesis of Zinc Aluminate Nanoparticles for CO and Propane Sensing Applications. Chemosensors 2023, 11, 105. https://doi.org/10.3390/chemosensors11020105
Likewise, after the XRD studies of the MgSb2O6, the following step consisted in analyzing the microstructure of the compound calcinated at 700 °C through SEM (see Figure 3). For this analysis, it was necessary to observe the different zones of the material to identify the morphology type obtained and the constitution of the particle size of our material. In our case, we found diverse morphologies (microrods, microsheets and particles with no apparent shape) and particle sizes. Taking the SEM images incorporated to the manuscript was base (see Figure 3a-c), the sizes of the microrods, microsheets and identified irregular particles were estimated. To obtain a clearer idea of the microstructure sizes, a particle size distribution histogram was added (see Figure 3d). An analysis and detailed description of the SEM images from was incorporated in the section 3.2 SEM analysis of our updated paper.
- Why did the author choose 400°C as the operating temperature? How about the sensing performances at higher or lower temperature?
Response: This is a great discussion question. During the sensing tests in environments of O2, C3H8, and CO2, several experiments were carried in different work conditions, amongst them the operation temperature was changed different scales, 300, 350, 400 and 450 °C, finding the best results at a 400 °C temperature. We experimentally observed that if the thick films were submitted to 300 and 350 °C temperature, the dynamic response of the material presented thermic instability and erroneous values in its electric resistance. Furthermore, these temperatures presented erroneous response and recovery times due to its lack of reproducibility. These parameters were unfavorable for the objectives of this paper in the development of a gas sensing technology. Likewise, when the measurements were made at 450 °C, the obtained cycles presented linearity due to an oversaturation of the test gases, i.e., the resistance changes were unstable in those working conditions. On the contrary, when the experiments were performed at 400 °C, the obtained curves presented a great stability, efficiency and capacity to detect the test gases (O2, C3H8, and CO2). For this reason, our workgroup took the decision of researching the dynamic response of the MgSb2O6 thick films in the O2, C3H8, and CO2 gases at temperature of 400 °C. To strengthen our response in this point, the section 3.3 Gas sensing properties analysis incorporated more information and a detailed description regarding the dynamic response and selectivity for the MgSb2O6 sensor with the O2, C3H8, and CO2 gases (see Figures 4 and 5).
- How about the influences of relative humidity
Response: This is a good commentary from the reviewer. In this question, it can be mentioned that currently our measurement system does not count with the capacity to perform humidity measurements or measurements of any other vapor types such as the alcohols. Currently, our gas sensing equipment can only perform studies of the gases proposed in this paper (O2, C3H8 y CO2). We consider doing a humidity study in our sensor is important. Therefore, and taking in considering the valuable commentary of the reviewer, our workgroup will be tasked of enhancing and updating our measurement system to perform humidity tests, along with other toxic gases in future investigations regarding the field of materials applied as gas sensors.
Author Response File: Author Response.docx
Reviewer 3 Report
Comments and Suggestions for AuthorsReviewer comments on the manuscript entitled " Design, simulation and construction of a O2 and C3H8, CO2 gas detection system based on the electrical response of the MgSb2O6 oxide.” the prototype of a gas detector based on the electrical response of the MgSb2O6 oxide at 400ºC temperature and with a concentration of 1000ppm was designed, simulated and fabricated.
The paper is worth for publishing after Minor Revisions. Detailed suggestions are posed below. Comments to the author(s):
1. The gas sensors of MgSb2O6 oxide have been investigated. Authors need to create tables to compare the work of others based on the materials.
2. Response-recovery time is also a very important parameter in gas sensing process, so the response-recovery time of the sensor should be listed.
3. Proving the strong influence of humidity on the responses of the proposed sensor. The authors should indeed consider these points in their manuscript.
4. Please give the details for preparing the target gases, including all gases.
5. Selectivity is a very important parameter for practical application, please provide Selectivity of the sensor to NO2, H2S et al these toxic gas.
6. The sample's composition and crystal structure should be examined by using X-ray diffraction. Please provide the XRD pattern of the synthesized material? And show the standard XRD PDF card number of the MgSb2O6.
Author Response
- The gas sensors of MgSb2O6 oxide have been investigated. Authors need to create
tables to compare the work of others based on the materials.
Response: This is a very good observation. In the improved version of the manuscript, our results were compared against similar (or equal) semiconductive oxides to those present in this paper, highlighting the improvements of our results with those reported in the literature for the same compound (or similar oxides). This information was added in section 3.3 Gas sensing properties analysis. Furthermore, to perform this comparison, new references were cited in the manuscript to sustain our response to this point. The new references are referred in the paper citations (refer to references 31, 34, 41, 56, 57).
- Response-recovery time is also a very important parameter in gas sensing process,
so the response-recovery time of the sensor should be listed.
Response: We agree with the reviewer in this part. The response and recovery times are very important to considerate a material as a gas sensor. In that sense, in the improved version of our manuscript, an extensive discussion of the obtained experimental sensing results on O2, C3H8 and CO2 environments (see 3.3 Gas sensing properties analysis) was performed. In the discussion section, the gas sensing results are displayed in Figure 4, the electric resistance change parameters for each gas were added. Based in the obtained results and the literature, the response and recovery times were calculated for each gas studied in this paper (O2, C3H8 y CO2). To estimate the response and recovery times for MgSb2O6, the conditions reported in reference 42 were employed, where 90% of the gas (O2, C3H8 and CO2 in our case) response is considered and only 10% of the gas (argon and air in our case) deployed to stabilize the film surfaces. The citation employed for the calculation of the response and recovery times can be found in our references with the following number:
- K. Arshak E. Moore G.M. Lyons J. Harris and S. Clifford. A review of gas sensors employed in electronic nose applications. Sensor Review, 24 2004, 181-198.
- Proving the strong influence of humidity on the responses of the proposed sensor. The authors should indeed consider these points in their manuscript.
Response: This is a great observation and a good point to take in consideration. Currently, our measurement system is not equipped to perform measurements of humidity or any other kind of vapors (such as alcohol) since it was thought to perform studies of the gases proposed in our manuscript. Additionally, our research group has planted to perform studies about other gases and vapor (and humidity) in the near future. It is a matter of economic of whether our workplace provides the necessary economic resources or not. Nonetheless, we consider the opinion of the reviewer to be of great importance and we will take the task of improving our system to consider the reviewer’s commentary in our future investigations in the field of gas sensors.
- Please give the details for preparing the target gases, including all gases.
Response: We are in concordance with the reviewer. In our updated manuscript, we have incorporated new information where the methodology and parameters employed to perform the measurements in the O2, C3H8 and CO2 environments are described. This new information was added in the newly added section 3.3 Gas sensing properties analysis. Furthermore, this in this section an extensive discussion regarding the gas sensing results (Figure 4) was incorporated to explain in detail the results registered in this work.
- Selectivity is a very important parameter for practical application, please provide Selectivity of the sensor to NO2, H2S et al these toxic gas.
Response: We agree with the reviewer. Unfortunately, our system does not count with the required instrumentation and it is inadequate to perform experiments with the atmospheres and vapors such as the aforementioned by the reviewer. Currently, our equipment can only perform test in O2, C3H8 and CO2 atmospheres. Based in the commentary of the reviewer, selectivity measurements of the O2, C3H8 and CO2 gases were performed. According to these results, an extensive discussion to verify which gas is the most selective over the thick films of MgSb2O6. These selectivity results can be corroborated and consulted in Figure 5 of the section 3.3 Gas sensing properties analysis.
It is worth noting that our workgroup will try to adjust our measurement system to perform tests and measurements of the semiconductive oxides we are researching to the environments mentioned by the reviewer. This with the purpose to perform a selectivity comparison between the gases.
- The samples composition and crystal structure should be examined by using X-ray diffraction. Please provide the XRD pattern of the synthesized material? And show the standard XRD PDF card number of the MgSb2O6.
Response: This is a very meaningful commentary and observation for our paper. Ergo, we are in agreement with the reviewer. In the improved version of our manuscript, we incorporated an x-ray diffraction pattern of the oxide identified in Figure 2 (see 3.1 XRD analysis) and the result was described in detail. The peaks obtained from this diffractogram calcinated at 700 °C, were indexed and compared with the database found in PDF No 88-1725. According to the database letter, we found that MgSb2O6 the belongs to the family of materials with a crystalline structure trirutile type with a spatial group of P42/mnm. The cell parameters of this compound were found in a = 4.64 Å and c = 9.25 Å, respectively. These results were compared with those performed in other studies that have reportedly synthetized the same compound, we found or x-ray diffraction pattern on Figure 2 is consistent with those found by other authors preparing MgSb2O6 through other synthesis methods. Additionally, we took in consideration the compound’s diffractogram to calculate the crystal size that constitutes the MgSb2O6. For this calculation, Scherrer’s equation was employed (see reference [35]):
- Gildo-Ortiz, L.; Rodríguez-Betancourtt, V.-M.; Ramírez Ortega, J.A.; Blanco-Alonso, O. An Alternative Approach for the Synthesis of Zinc Aluminate Nanoparticles for CO and Propane Sensing Applications. Chemosensors2023, 11, 105. https://doi.org/10.3390/chemosensors11020105
Author Response File: Author Response.docx