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Article

Selective NO2 Detection by Black Phosphorus Gas Sensor Prepared via Aqueous Route for Ship Pollutant Monitoring

by
Yang Wang
,
Yujia Wang
,
Yue Sun
,
Kuanguang Zhang
,
Chenyang Zhang
,
Jianqiao Liu
*,
Ce Fu
* and
Junsheng Wang
*
College of Information Science and Technology, Dalian Maritime University, Dalian 116026, China
*
Authors to whom correspondence should be addressed.
J. Mar. Sci. Eng. 2022, 10(12), 1892; https://doi.org/10.3390/jmse10121892
Submission received: 29 October 2022 / Revised: 23 November 2022 / Accepted: 23 November 2022 / Published: 4 December 2022
(This article belongs to the Special Issue Advances in Sensor Technology in Smart Ships and Offshore Facilities)
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Abstract

:
The emission of nitrogen dioxide (NO2) caused by marine transportation has attracted worldwide environmental concerns. Two-dimensional (2D) black phosphorus (BP) is an emerging semiconductive material with the advantages of high electron mobility, a layer-dependent direct band gap and a large specific surface area. These properties ensure excellent potential in gas-sensing applications. In this work, BP quantum dots (QDs) are synthesized from commercial red phosphorus (RP) fine powder via the aqueous route. The BP QDs show uniform size distribution with an average size of 2.2 nm. They are employed to fabricate thin film gas sensors by aerial-assisted chemical vapor deposition. The microstructure, morphology and chemical composition are determined by various characterizations. The sensor performances are evaluated with the optimized response set to 100 ppm NO2 of 10.19 and a sensitivity of 0.48 is obtained. The gas sensor also demonstrates excellent repeatability, selectivity and stability. The fabricated thin film gas sensor assembled by BP QDs exhibits prospective applications in selective NO2 detection for marine gaseous pollutant monitoring and control.

1. Introduction

The rapid development of marine transportation driven by growing global trade and economic activities leads to a huge amount of gaseous pollutant emissions into the atmosphere [1]. Among them, nitrogen dioxide (NO2) is considered a priority impactive pollutant as it may lead to acid rain, eutrophication, acidity of surface water and, consequently, toxicity to living creatures [2,3,4,5,6,7,8,9]. Therefore, the monitoring of ship exhausts, especially nitrogen dioxide emission, has attracted worldwide environmental concerns.
Two-dimensional (2D) nanostructures are emerging candidates for developing semiconductor gas sensors with superior properties [10,11,12,13]. Compared to traditional gas sensors involving semiconductor bulks, the 2D nanostructures have the advantage of a large specific surface area, abundant active dangling bonds, and high carrier mobility [14]. Among 2D materials, such as transition metal dichalcogenides [15], graphic-like carbon nitrides (g-C3N4) [16], reduced-graphene oxide (rGO) [17], hexagonal-boron nitride (h-BN) [18], and transition metal carbide [19], black phosphorus (BP) is attractive due to the controllable direct band gap, free of metal elements and biocompatibility [20,21,22,23,24,25]. These unique properties provide great potential and suitability in applications of high-performance electronic components [26,27], photocatalysis [28,29] and medical treatments [30,31].
The BP-based nanostructures were soon put into the development of gas sensors. M. Donarelli’s early work prepared exfoliated BP flakes for an NO2 gas sensor, but the performance was quite low [32]. G. Lee used suspended BP flakes and the device showed a response of 2.86 to 200 ppm target gas [33]. To improve the performance of BP-based gas sensors, Ag-decorated BP nanosheets were prepared by Y. Wang [34] and an Au incorporation into the BP matrix was completed by S. Cho [35]. Thus, the limit of detection (LOD) was significantly lowered to sub-ppm level. The combination of BP nanostructures with other semiconductors was also developed to construct heterojunctions for improved sensor performances [36,37,38,39].
However, the synthesis of BP nanostructures and the fabrication of their subsequent electronic devices were rather complex. Mechanical exfoliation was the most popular method in the early stages. The BP bulk, which was stacked by phosphorene connected by Van der Waals force, was exfoliated mechanically, e.g., by tapes. The obtained few-layer BP structures were cleaned using organic solvents and sent for the fabrication of gas sensors on substrates. For instance, by using these procedures, Cui prepared a field-effect transistor sensor device based on BP nanosheets, which showed a response of 1.9 to 20 ppb NO2 with good repeatability [40]. Similarly, Lee’s work reported the platinum functionalization of BP gas sensors, which exhibited a response of 1.6 to 4000 ppm H2 at 100 °C [41]. Nevertheless, the mechanical exfoliation required by specific facilities were unable to be operated under ambient conditions, restricting the yield of BP nanostructures. Another technique that developed later was liquid exfoliation, which used ultrasonic facilities to destroy the layered structure of bulk BP. This method was successful in providing a high yield of BP nanostructures but it required the extensive usage of organic solvents, where the BP bulk was disassembled. Chen exfoliated BP bulk into highly-dispersed BP nanosheets in N-methylpyrrolidone and fabricated BP-based gas sensors, but the response was unsatisfactory [42]. Wang synthesized BP nanosheets from bulk in diethylene glycol dimethyl ether by ultrasonication in ice water and the obtained nanostructures were used to prepare BP-based gas sensors, which demonstrated a fast response and recovery [43]. However, the liquid exfoliation was facing fatal drawbacks of non-uniform size and morphology as well as an uncontrollable nanostructure. Despite the excellent properties and great potential of BP-based gas sensors, their practical application was restricted by complicated and expensive synthesis procedures. A simple synthesis technique for BP nanostructures with environmental and cost considerations is expected.
In this work, a facile aqueous synthesis of BP quantum dots (BP QDs) from commercial red phosphorus (RP) is developed without using toxic and explosive organic solvents. The BP QDs are used to fabricate thin film gas sensors for NO2 detection by aerial-assisted chemical vapor deposition (AACVD). The BP QDs and their subsequent thin films are characterized in the aspects of microstructure, morphology and elemental compositions. The optimized deposition conditions of thin films are concluded and the gas-sensing performances of response, sensitivity, repeatability, selectivity and stability are evaluated. The gas-sensing mechanism of BP thin films in NO2 detection is also interpreted.

2. Materials and Methods

2.1. Aqueous Preparation of BP

All chemicals used in this work are analytical reagents obtained from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). The BP QDs were synthesized via a one-step aqueous route [44], which is illustrated in Figure 1.
The initial RP was cracked and passed through a mesh to obtain an RP fine powder with a particle size less than 106 μm. The RP fine powder of 0.2 g was dispersed by 16.2 mL deionized water (DI) in a polyphenylene autoclave, which was sent for hydrothermal treatment, conducted at 200 °C for 48 h before cooling to room temperature. After this process, the RP fine powder was transformed into BP QDs in the aqueous solution.

2.2. Deposition of BP Gas Sensors

The BP gas sensors were fabricated by using the AACVD method [45], which is illustrated in Figure 2. The alumina substrates, on which a pair of Ag interdigital electrodes were designed, were cleaned and placed in the tube. The BP QD aqueous solution was atomized and delivered by the N2 carrier gas with a flux of 100 sccm into the tube. The deposition was conducted at 250–450 °C and, thus, the BP thin films were obtained after the QDs were deposited on the alumina substrates.

2.3. Characterization

A high-resolution transmission electron microscopy (HRTEM, JEM-2100F, JEOL, Tokyo, Japan) and X-ray diffraction (XRD, D/Max-Ultima, Rigaku, Tokyo, Japan) were used to observe the microstructural properties of the BP QDs. The surface chemical characteristics were collected via X-ray photoelectron spectroscopy (XPS, ESCALAB 250XI, Thermo Fisher Scientific, Waltham, MA, USA). The surface morphology and compositional mappings of the BP thin film sensors were evaluated via scanning electron microscopy (SEM, ZEISS Gemini 500, Carl Zeiss AG, Oberkochen, Germany) with the component of energy dispersive spectroscopy (EDS). The BP QD aqueous solution was used in the HRTEM characterization. The BP containing solution was sprayed onto quartz pieces and dried in an oxygen free atmosphere before XPS and EDS analyses. The BP thin film gas sensors were sent to SEM observation after the AACVD procedures.

2.4. Measurement of Gas-Sensing Properties

All evaluations of the sensor performance of the BP thin film were conducted at room temperature (25 °C) and a relative humidity (RH) of 40%, except for the humidity dependence evaluation. High purity (>99%) gases of C4H10, H2, H2S and NO2 were used as target gases. A computer-controlled gas-sensing measurement system [46,47] was used to collect the resistance of the BP thin films. The response (S) was defined as the resistance change of the sensor after gas exposure, calculated by S = Ra/Rg, where and Ra and Rg were the resistance in the air and in the target gas, respectively. The response time (Tres) and recovery time (Trec) were defined as the times needed for the gas sensor to reach 90% resistance variation after injection or removal of the target gas. The sensitivity indicated the sensor response led by the unit change in gas concentration. Mathematically, it was calculated by the slope (n) of the response against the gas concentration in the logarithmic coordinates, as n = lnS/lnC.

3. Results and Discussion

3.1. Characterization of BP QDs

The microstructural properties and morphology of the as-synthesized BP QDs is shown in Figure 3. The HRTEM observation in Figure 3a shows that the BP QDs are of good dispersion in aqueous solution. Figure 3b demonstrates the size distribution of BP QDs, which indicates that the average size is approximately 2.8 nm. The high-resolution lattice fringes are clearly exhibited in Figure 3c. The fringe spacing of 0.21 nm is revealed and is associated with the (021) facet of the BP crystal lattice [48]. The XRD pattern of BP QDs is revealed in Figure 3d. The sole peak at 27.3° is observed, corresponding to the (021) facet of the BP lattice structure as listed in the standard pattern of JCPDS 01-076-1967 [49]. The broad shape of the peak infers the tiny crystallite structure of the BP QDs. Based on the Debye–Scherrer equation, the crystallite size is evaluated to be 2.5 nm, close to the HRTEM observation.
Figure 4a demonstrates the XPS survey spectrum of the BP thin films. All of the peaks are calibrated using the C peak at 284.8 eV [50,51]. The survey spectrum demonstrates the presence of P, O, Si, N and C. The tiny nitrous signal is ascribed to the impurities led by the N2 carrier gas during the deposition process, while the Si peak is caused by the quartz substrates used in the XPS characterizations. The high-resolution spectrum for the P element is revealed in Figure 4b, where double peaks at 130.48 eV and 134.78 eV are observed. The former one is assigned to the P 2p peak [52] while the latter one is ascribed to the phosphorus oxide (POX) [53]. Thus, the as-synthesized BP QDs in aqueous solution are partially-oxidized. The O spectrum is exhibited in Figure 4c and is composed of double peaks at 531.78 eV and 532.18 eV. The high intensity peak is ascribed to the O-P-O bonds and the other one is caused by the bivalent bond (P=O) in oxidized phosphorus. Apart from the surface bonding properties evaluated by the XPS, the bulk composition of the BP QDs is analyzed by EDS, as shown in Figure 4d. The main signals of phosphorus and oxygen are detected together with silicon in the quartz substrates. The peak area proportion of each element is employed to evaluate the elemental composition of the sample. After deducting the stoichiometric O atoms of SiO2 in the quartz substrate, the P/O ratio is calculated to be 1.6, inferring that 1/4 of the P atoms in the BP structure are in the oxidizing state.

3.2. Characterizations of BP Gas Sensors

The surface morphology of the gas sensor deposited by the BP QDs is revealed in Figure 5a,b, where BP grains of 100–500 nm are uniformly scattered on the substrate. The average grain size is evaluated to be 310 nm. The scattered distribution of the BP grains provides a large specific surface area with rich active sites for gas absorption, which is constructive for the enhancement of the gas-sensing properties. Figure 5c–e demonstrate the surface composition of the BP thin film sensors. P and O are detected and they show spatial uniformity. The existence of O comes from the partial oxidation of the as-prepared BP QDs. The partial oxidation of the thin film surface may protect the inner part and prevent further oxidation during gas detection in ambient condition [54,55]. This is beneficial for permanent stability of BP thin films.

3.3. Gas-sensing Properties

The gas sensors are tested under the exposure of 100 ppm NO2. Figure 6a exhibits the kinetic response of the BP thin films deposited for 30 min at the temperatures of 250, 300, 350, 400 and 450 °C. The Tres and Trec are 36 s/162 s, 51 s/565 s, 38/844 s, 91 s/174 s and 48 s/108 s, respectively. The sensor responses are 1.56, 2.49, 10.19, 1.41 and 1.07, respectively, as shown in Figure 6c together with their initial resistances in air. It is observed that the BP thin film deposited at 350 °C has an optimized response and response time. The dependence of gas-sensing properties on deposition time is also illustrated in Figure 6b, in which the BP thin film is deposited at 350 °C. The deposition times of 15–75 min were conducted and the Tres/Trec of the thin films were 123 s/223 s, 38 s/844 s, 40 s/103 s, 89 s/95 s and 100 s/516 s, respectively. The sensor responses of 1.22, 10.19, 4.18, 1.64 and 1.40 are observed, respectively, as shown in Figure 6d, together with their initial resistances in air. The optimum gas-sensing performances were obtained for the BP thin film deposited at 350 °C for 30 min. This optimized deposition condition was used in the successive preparation of the BP gas sensors.
Figure 7a shows the dynamic response of the BP gas sensor deposited at 350 °C for 30 min to various concentrations of NO2 gas. The resistance of the BP thin film responds to the exposure to target gas of 20–100 ppm and has a complete recover ability. The sensor responses are calculated and plotted in both of the linear and logarithmic coordinates, as shown in Figure 7b. The response against the gas concentration follows the power law [56,57], which describes the saturation effect of sensors in a high concentration of target gas. Based on the logarithmic relation, the sensitivity is evaluated to be 0.48, which infers that the thin film gas sensor deposited by the BP QDs has excellent gas-sensing performance. The theoretical LOD of the BP gas sensor is evaluated to be 0.54 ppm, based on the root-mean square deviation (RMSD) and sensitivity, according to LOD = 3 × RMSD/sensitivity [34].
Repeatability and selectivity are the other two fundamental properties for gas sensors. Figure 8a demonstrates the repeatability test of the BP gas sensor, which exhibits a consistent response to 100 ppm NO2 among four cycles of 800 s. The selectivity test is conducted by using the target gases NO2, H2S, H2 and C4H10. The response to the four types of gases at 20 and 100 ppm are shown in Figure 8b. As the p-type nature of BP thin film, the sensor shows a response below 1 when reducing H2S gas is tested. Meanwhile, the BP thin film is insensitive to H2 and C4H10. The dependence of sensor performance on humidity is shown in Figure 8c, where a slight decrease in response is observed, showing that the BP thin film shows good stability against humidity. The insensitive RH dependence could be ascribed to the partially-oxidized surface of the BP thin film. Nevertheless, humidity corrections or compensations could be carried out if precise detection is required. The sensor resistance in this work is in the range of 10–50 MΩ, which is at the same level with sensors from previous works [58]. The time-dependent resistance of thin film is evaluated within 30 days. As shown in Figure 8d, the sensor resistance demonstrates general stability over time. A minor increase in resistance is observed after 10 days and this could be due to further slight oxidation of the BP thin films. Therefore, the as-prepared BP thin film gas sensor demonstrates excellent repeatability, selectivity and stability in the detection of NO2 gas. The NO2 sensing performance of the BP-based gas sensor is compared in Table 1. The present BP thin film gas sensor has superior gas-sensing properties to other published devices.

3.4. Gas-Sensing Mechanism

The development of BP gas sensors will benefit if the process of gas detection is well understood. Figure 9 demonstrates the gas-sensing mechanism of BP gas sensors. When the BP is exposed to NO2, the oxidizing gas species will adsorb on the surface of the BP grains. The adsorbates of NO2− capture electrons from the P atoms on the grain surface, resulting in the decrease of electron density as well as the increase in hole density. As the p-type characteristics of BP, the sensor resistance is decreased, exhibiting an electrical response to NO2 gas. On the other hand, when NO2 gas is removed from the atmosphere, the BP thin film desorbs the NO2- species and the electrons that were seized by the adsorbates are returned to the semiconductor. Thus, the resistance of the BP thin film recovers to the initial value.

4. Conclusions

BP QDs were synthesized in an aqueous solution via a one-step hydrothermal method. They were employed to fabricate BP thin film using the AACVD technique. The microstructural, morphological and compositional properties of the BP QDs and thin films were evaluated by HRTEM, XRD, XPS, SEM and EDS characterizations. Several conclusions were drawn as follows:
  • The BP QDs were prepared from RP fine powder under low temperature, without using any toxic or explosive organic solvents.
  • The BP thin films deposited from QDs exhibited good gas-sensing performance and optimized sensor properties were obtained from the BP gas sensors deposited at 350 °C for 30 min.
  • The optimum response to 100 ppm NO2 was 10.19 with a sensor sensitivity of 0.48. The BP thin film gas sensor also demonstrated excellent recovery ability, repeatability, selectivity and stability. The present BP thin film gas sensor has superior gas-sensing properties to other published devices.
This work not only accomplished the design of a BP thin film gas sensor with promising prospects for the selective detection of gaseous ship pollutants, but also contributes to a green strategy for the fabrication of 2D BP-based semiconductor devices.

Author Contributions

Conceptualization, Y.W. (Yang Wang) and J.L.; methodology, Y.W. (Yujia Wang), Y.S., K.Z. and C.Z.; investigation, Y.S., K.Z. and C.Z.; writing—original draft preparation, Y.W. (Yang Wang) and J.L.; writing—review and editing, C.F. and J.W.; project administration, C.F. and J.W.; funding acquisition, J.L. All authors have read and agreed to the published version of the manuscript.

Funding

This work is financially supported by the International Science & Technology Innovation Program of the Chinese Academy of Agricultural Sciences (Grant No. CAAS-ZDRW202110), the Scientific Research Funding Project of the Educational Department of Liaoning Province (Grant No. LJKZ0060), the Liaoning Applied Fundamental Research Project (Grant No. 2022JH2/101300158) and the Fundamental Research Funds for the Central Universities (Grant No. 3132022238).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Acknowledgments

We appreciate Eceshi (www.eceshi.com (accessed on 25 October 2022)) for the XRD and XPS characterizations.

Conflicts of Interest

The authors declare no conflict of interest.

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Jmse 10 01892 g001 550
Figure 1. Aqueous preparation procedure of BP QDs from RP via the hydrothermal method.
Figure 1. Aqueous preparation procedure of BP QDs from RP via the hydrothermal method.
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Figure 2. AACVD procedure of BP thin film gas sensors.
Figure 2. AACVD procedure of BP thin film gas sensors.
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Jmse 10 01892 g003a 550Jmse 10 01892 g003b 550
Figure 3. Microstructural properties of BP QDs in aqueous solution: (a) Morphology; (b) High-resolution lattice fringes; (c) Size distribution; (d) XRD pattern.
Figure 3. Microstructural properties of BP QDs in aqueous solution: (a) Morphology; (b) High-resolution lattice fringes; (c) Size distribution; (d) XRD pattern.
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Jmse 10 01892 g004a 550Jmse 10 01892 g004b 550
Figure 4. Compositional properties of BP QDs: (a) XPS survey spectrum; (b) XPS P 2p spectrum; (c) XPS O 1s spectrum; (d) EDS spectrum.
Figure 4. Compositional properties of BP QDs: (a) XPS survey spectrum; (b) XPS P 2p spectrum; (c) XPS O 1s spectrum; (d) EDS spectrum.
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Figure 5. Microstructural and compositional properties of the BP thin film sensor: (a) SEM morphology; (b) SEM morphology with size distribution of grains; (c) Local morphology for elemental mapping; (d) Elemental distribution of P atoms; (e) Elemental distribution of O atoms.
Figure 5. Microstructural and compositional properties of the BP thin film sensor: (a) SEM morphology; (b) SEM morphology with size distribution of grains; (c) Local morphology for elemental mapping; (d) Elemental distribution of P atoms; (e) Elemental distribution of O atoms.
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Figure 6. Gas-sensing properties of BP thin films: (a) Thin films deposited under various temperatures; (b) Thin films deposited under various times; (c) Influence of deposition temperature; (d) Influence of deposition time.
Figure 6. Gas-sensing properties of BP thin films: (a) Thin films deposited under various temperatures; (b) Thin films deposited under various times; (c) Influence of deposition temperature; (d) Influence of deposition time.
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Figure 7. Gas-sensing properties of BP gas sensors deposited at 350 °C for 30 min: (a) Dynamic sensor response to various gas concentrations; (b) Evaluation of sensor sensitivity.
Figure 7. Gas-sensing properties of BP gas sensors deposited at 350 °C for 30 min: (a) Dynamic sensor response to various gas concentrations; (b) Evaluation of sensor sensitivity.
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Figure 8. The repeatability, selectivity and stability evaluation of BP thin films deposited at 350 °C for 30 min: (a) Repeatability test; (b) Selectivity test; (c) RH dependence; (d) Resistance stability over time.
Figure 8. The repeatability, selectivity and stability evaluation of BP thin films deposited at 350 °C for 30 min: (a) Repeatability test; (b) Selectivity test; (c) RH dependence; (d) Resistance stability over time.
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Figure 9. Schematic drawing of the gas-sensing mechanism of the BP sensor to NO2.
Figure 9. Schematic drawing of the gas-sensing mechanism of the BP sensor to NO2.
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Table
Table 1. Comparison of NO2 sensing performances of the BP-based gas sensors.
Table 1. Comparison of NO2 sensing performances of the BP-based gas sensors.
ReferenceCompositionConcentration
(ppm)		Operating
Temperature
(°C)		Response
[32]BP flakes0.2251.08
[33]BP flakes200N/A2.86
[34]Ag-decorated BP0.1221.67
[35]Au-incorporated BP1253.33
[36]Co3O4-PEI-BP3252.86
[37]ZnO-BP0.05253.85
[38]SnS2-BP0.1256.08
[39]MXene-BP10201.24
This workBP thin film1002510.19
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Wang, Y.; Wang, Y.; Sun, Y.; Zhang, K.; Zhang, C.; Liu, J.; Fu, C.; Wang, J. Selective NO2 Detection by Black Phosphorus Gas Sensor Prepared via Aqueous Route for Ship Pollutant Monitoring. J. Mar. Sci. Eng. 2022, 10, 1892. https://doi.org/10.3390/jmse10121892

AMA Style

Wang Y, Wang Y, Sun Y, Zhang K, Zhang C, Liu J, Fu C, Wang J. Selective NO2 Detection by Black Phosphorus Gas Sensor Prepared via Aqueous Route for Ship Pollutant Monitoring. Journal of Marine Science and Engineering. 2022; 10(12):1892. https://doi.org/10.3390/jmse10121892

Chicago/Turabian Style

Wang, Yang, Yujia Wang, Yue Sun, Kuanguang Zhang, Chenyang Zhang, Jianqiao Liu, Ce Fu, and Junsheng Wang. 2022. "Selective NO2 Detection by Black Phosphorus Gas Sensor Prepared via Aqueous Route for Ship Pollutant Monitoring" Journal of Marine Science and Engineering 10, no. 12: 1892. https://doi.org/10.3390/jmse10121892

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