Cataluminescence gas sensor for ketones based on nanosized NaYF4:Er

Cataluminescence gas sensor for ketones based on nanosized NaYF4:Er

Sensors and Actuators B 222 (2016) 300–306 Contents lists available at ScienceDirect Sensors and Actuators B: Chemical journal homepage: www.elsevie...

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Sensors and Actuators B 222 (2016) 300–306

Contents lists available at ScienceDirect

Sensors and Actuators B: Chemical journal homepage:

Cataluminescence gas sensor for ketones based on nanosized NaYF4 :Er Jie Tang, Hongjie Song, Binrong Zeng, Lichun Zhang ∗ , Yi Lv Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China

a r t i c l e

i n f o

Article history: Received 13 April 2015 Received in revised form 4 August 2015 Accepted 11 August 2015 Available online 20 August 2015 Keywords: NaYF4 Gas sensor Cataluminescence Ketones Dope

a b s t r a c t A novel gas sensor toward ketones based on cataluminescence generated on the surface of nanosized NaYF4 :Er was developed. The sensing materials NaYF4 :Er was synthesized by a simple hydrothermal method and characterized by powder X-ray diffraction, scanning electron microscope and energy dispersive X-ray spectroscopy. The effect of Er3+ doping concentration and crystallinity of NaYF4 :Er on the CTL intensity were studied. When the Er3+ doping concentration reaches 20%, the materials show excellent sensing characteristics for ketones. Under the optimal experimental conditions, as represented by the acetone and butanone, the gas sensor has fast responses (3 s) and relatively low work temperature (250 ◦ C). The linear range of cataluminescence intensity versus concentration were 2.388–143.28 ␮g mL−1 for acetone and 2.45–49.0 ␮g mL−1 for butanone, with a detection limit (signal-to-noise ratio is 3) of 1.7 ␮g mL−1 and 0.7 ␮g mL−1 , respectively. Foreign 11 substances in common have little interference which indicates the high selectivity of the CTL sensor for ketones. © 2015 Elsevier B.V. All rights reserved.

1. Introduction Volatile organic compounds (VOCs) are usually emitted as a result of human activities and always used in industrial and domestic activities [1,2]. More seriously, some VOCs are directly harmful (carcinogenetic, nervously paralyzed, uncomfortable, etc.) and cause some social destructions such as ozone hole destruction, green house effect and so on [3]. As one of volatile organic compounds, ketones are the most common reagent in biological chemistry and frequently used as solvent and polymer in industry and pharmaceutical production, especially acetone and butanone. People may develop a headache, fatigue, and even narcosis when the concentration of acetone is high in the air. Acetone levels in diabetic patients’ blood and spittle are higher than those of healthy people [4]. A certain concentration of butanone had some stimulative on our eyes and throat. Therefore, it is desirable to establish a sensing platform for on-site and real-time monitoring of ketones. Recently, scientists have been committed to explore more analytical methods for detection of ketones, such as semi-automated enzymic assay [5], HSCC-UV-IMS [6], high-performance liquid chromatography [7] and dual-wavelength detection [8], etc. All of these techniques inherit merits of high performance and sensitivity for trace acetone, while they meet the intrinsic defects that online monitor the contamination in actual locale is hard to achieve.

∗ Corresponding author. Tel.: +86 28 85412398; fax: +86 28 85412398. E-mail address: [email protected] (L. Zhang). 0925-4005/© 2015 Elsevier B.V. All rights reserved.

Hence, it is necessary to seek stable, simple and portable sensors for ketones. Cataluminescence (CTL) is CL generated on the surface of solid catalysts during the catalytic oxidation of organic vapors in an atmosphere containing oxygen. Due to the stable intensity, simple implementation, high sensitivity, and rapid response, CTL gas sensors have received significant research attention. Since 1990, Nakagawa et al. [9,10] have poured much endeavor on the CTL studies and established a series of gas sensing systems. They developed a series of CTL gas sensors with bulk ␥-Al2 O3 as sensing materials to determine vapors of ethanol, butanol [11]. In the last decades, the application of nanomaterials has greatly driven the development of CTL analysis owning to their high surface areas, good adsorption characteristics, high catalytic activity [12,13]. Both Zhang et al. [14,15] and Zhu et al. [16,17] have been engaged in development of a series of different catalytic nanomaterials for CTL gas sensors. In 2002, Zhang et al. [18] firstly utilized nanosized TiO2 as sensing material to design an acetone and ethanol CTL sensor. After that, various nanomaterials have been attracted widespread attention in the field of catalysis. More recently, Zhang et al. [19] using different nanomaterials assembled a catalytic optical chemo-sensor array for the CTL discrimination of ethanol, hydrogen sulfide, and trimethylamineon. Besides, our group is also devoted to expanding the range of application of nanomaterials in developing CTL sensors [20–22]. Through controllable synthesis of catalysts with special uniform morphologies and doping method, our group has explored great many CTL sensors with better selectivity, high sensitivity, and fast response. For example, we have controllably synthesized Mn3 O4 micro-octahedra and hexagonal nanoplates with excellent CTL sensing characteristics for acetone [23]. Recently Y-doped

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metal-organic framework-5 synthesized by a simple solvothermal method was used as a CTL material to detect isobutanol [24]. With special properties, reliable optical applications and enhanced catalytic performances, rare earth compounds were widely used in electric, magnetic, optical, and catalytic fields [25]. Furthermore, originating from unique 4f electrons of rare earth ions, doping rare earth ions into materials inherits special properties such as reliable optical applications and enhanced catalytic performances. For instance, the CTL at 620 nm from Eu3+ doped in nanosized ZrO2 shows 72 times higher sensitivity than the CTL at 460 nm from excited intermediates in the ethanol sensor [26]. Similarly, Eu3+ -doped YVO4 used as a CTL catalyst can improve sensitivity to detect ethanol [27], and ␥-Al2 O3 activated with Dy3+ was obtained with high sensitivity for hydrocarbon CTL gas sensors [28]. In consequence, rare earth ions are attractive to extensively apply in CTL to develop highly sensitive and selective sensors. In this work, we have synthesized NaYF4 nanocrystals doped with different concentrations Er3+ to improve the CTL sensing properties. A strong CTL emission could be observed when ketones vapor was delivered through the surface of the nanomaterials. Sensing tests showed that the proposed CTL sensor possessed not only good stability and high sensitivity, but also short response time and excellent selectivity to ketones. 2. Experiment 2.1. Reagents and material All chemicals were of analytical grade or better and were used as received without further purification. Sodium fluoride, yttrium oxide (Y2 O3 ), erbium oxide (Er2 O3 ), sodium hydroxide, ethanol and oleic acid are supplied by Chengdu Kelong Chemical Reagent Co. Ltd. (Chengdu, China). All aqueous solutions were prepared using ultrapure water (Mill-Q, Millipore, 18.2 M resistivity).


thoroughly stirred. Subsequently, the milky colloidal solution was transferred to a 50 mL teflon-lined autoclave, which was heated at 180 ◦ C for 24 h. The final products were collected by means of centrifugation, washed with ethanol and deionized water for several times. After dried in vacuum at 80 ◦ C for 4 h. NaYF4 nanocrystals doped with different concentrations of Er3+ were prepared by the same procedure except for varying the amount of Er2 O3 . 2.3. Characterization The crystal phase of NaYF4 :Er was identified by the powder X-ray diffraction (XRD, Philips Analytical, Netherlands) with a ˚ radiation. plumbaginous-monochromatized Cu K␣1 ( = 1.5406 A) The morphology of the samples was inspected using scanning electron microscopy (SEM, JSM-5900LV) at an acceleration voltage of 20 kV. And Energy-dispersive X-ray spectroscopy (EDS) was obtained on the same instrument to determine the elemental compositions of NaYF4: Er. 2.4. CTL sensing measurements The schematic diagram of the CTL gas sensor was shown in Scheme 1. About 0.03 g NaYF4 :Er, which was calcined in a muffle furnace at 400 ◦ C, were coated on a ceramic heating rod which was put in a quartz tube (i.d. = 10 mm and length = 100 mm). VOCs vapors were introduced into the sensing system by air flow, and the consequent CTL emission was recorded by a BPCL ultra-weak luminescence analyzer (BP-II, Institute of Biophysics, Academia Sinica, Beijing, China). The temperature of the heating rod was controlled by a digital controller and the flow rate of air was adjusted by a precision flow meter. 3. Results and discussion 3.1. Characterization

2.2. Preparation of materials NaYF4 :Er were synthesized according to previously reported method with some modifications [29]. In a typical synthesis process for NaYF4 :Er (20%), a mixture of 0.113 g Y2 O3 and 0.0383 g Er2 O3 (nY :nEr = 80:20) was dissolved in hot nitric acid (65 ◦ C) to acquire Ln(NO3 )3 , and the solvent was evaporated after 6 h reaction. 7 mL of NaF aqueous solution (1 mol/L) and 1 mL of Ln(NO3 )3 aqueous solution was added to the mixture of NaOH (1.2 g), ethanol (8 mL), deionized water (4 mL), and oleic acid (20 mL), and the solution was

All NaYF4 nanocrystals doped with different concentrations Er3+ were obtained consisting of a majority of cubic phase and a small amount of hexagonal phase, as demonstrated by the XRD pattern in Fig. 1. All diffraction peaks of the samples matched very well with cubic phase (JCPDS 39-0723) and hexagonal phase (JCPDS 16-0334). No other impurity peaks (e.g. Er2 O3 ) were detected. The EDS spectrum in Fig. 2a clearly revealed the presence of Er and other elements, which means that Er3+ were successfully doped into NaYF4 nanocrystals.

Scheme 1. Schematic diagram of the CTL sensing system.


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butanone were delivered by an air flow of 250 mL min−1 and 100 mL min−1 respectively with a series of optical filters in the range of 400–625 nm (400, 425, 440, 460, 490, 535, 555, 575 and 620 ± 10 nm) at the temperature of 250 ◦ C. As shown in Fig. 3, the highest response and signal to noise (S/N) of acetone and butanone were both observed at the wavelength of 490 nm. Thus, 490 nm as the optimal wavelength was chosen in the subsequent experiment. 3.3. Effect of Er3+ -doping concentration on the CTL intensity and possible mechanism

Fig. 1. XRD patterns of nanocrystals with different Er3+ -doping concentration on NaYF4 . , cubic phase (JCPDS file no. 39-0723); 䊉, hexagonal phase (JCPDS file no. 16-0334). Table 1 CTL responses and recovery times of different kind of ketones. Ketones





Response time (s) Recover time (s)

3 30

3 60

35 >440

20 >580

The size and morphology of the NaYF4 :Er nanocrystals were characterized by SEM. It’s worth noticing that NaYF4 :Er (20%) were chosen as an example. As shown in Fig. 2b and c, the cubic phase, which exhibited rectangular cubic-like morphology, and few of rod-like hexagonal phase were coexisted. All nanocubics were ∼40 nm in width, and the nanorods were ∼50 nm in diameter and ∼500 nm in length. 3.2. Cataluminescence responses of ketones on NaYF4 :Er As shown in Table 1, different kind of ketones such as acetone, butanone, cyclohexanone, acetylacetone, led to different CTL responses on the same conditions. Because the boiling point of cyclohexanone and acetylacetone were very high, it is difficult for them to completely vaporize in a short period of time and the catalytic oxidation continually occur with the process of evaporation. Therefore, the CTL signal of cyclohexanone and acetylacetone had the relatively longer response time and recovery time. For these many reasons, acetone and butanone were chosen as model analytes to study the CTL sensing characteristics. In order to search the proper detection wavelength for the maximum CTL signal, a concentration of 23.88 ␮g mL−1 acetone and 24.50 ␮g mL−1

To explore Er3+ -doping concentration affected the CTL intensity, four different levels of Er3+ -doped NaYF4 used as sensing materials to explore its effect on the CTL intensity. 23.88 ␮g mL−1 acetone and 24.50 ␮g mL−1 butanone were introduced and passed through the surface of different nanocrystals by the air flow of 250 mL min−1 and 100 mL min−1 , respectively, at 250 ◦ C at 490 nm. As shown in Fig. 4a, the CTL intensity was quite different under various Er3+ doping concentrations on NaYF4 , and 20% Er3+ doping concentration had the maximal CTL intensity. It is noteworthy that information on the crystallinity of the nanocrystals could be obtained from the width of the diffraction peaks [30]. As shown in Fig. 4b, the full width at half maximum (FWHM) was gradually narrowed as the Er3+ ion concentration increased up to 20%, and then broadened as the concentration further increased. The results indicated that the crystallinity of the nanoparticles was improved when the Er3+ ion concentration was lower than 20%, and reduced when the Er3+ concentration was greater than 20%. According to the literature [31], higher crystallinity of catalysts has a good effect on catalytic performance. Therefore we supposed that the doping concentration of Er3+ influenced the crystallinity of catalysts synthesized at the same condition, and high crystallinity of catalysts consequently improved the CTL intensity. So, further experiments for acetone and butanone detection were based on the catalyst of NaYF4 :Er (20%). According to the widely accepted theory of CL reactions, excited intermediates are formed during the reaction process. The emission of luminescence emission could be caused by excited intermediates falling to the ground state [32,33]. So, a possible mechanism of CTL with ketones on nanosized NaYF4 :Er (20%) can be deduced as follows: when ketones were introduced into the sensing system by air flow, it was catalytically oxidized by oxygen in the air, and then excited intermediates were formed during the reaction to generate CL when they return to their ground state. However the more exact mechanism awaits further exploration. 3.4. Effect of working temperature and gas flow rate on CTL Temperature is a key factor for catalytic oxidation reactions, in most cases; the activity of the catalyst generally increases with the temperature. In order to investigate the effect of temperature

Fig. 2. (a) EDS spectrum of each component in obtained rare earth compounds and (b) SEM images of catalysts: NaYF4 :Er (20%).

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Fig. 3. CTL spectra emission of (a) acetone and (b) butanone. Temperature, 250 ◦ C, and air flow rate, 250 mL min−1 and 100 mL min−1 , respectively. Error bars stand for ±S.D. (standard deviation).

on the CTL intensity, 23.88 ␮g mL−1 acetone and 24.50 ␮g mL−1 butanone were studied at different temperatures. The signal intensity and S/N versus the catalysis temperature under the wavelength of 490 nm at 250 mL min−1 and 100 mL min−1 air flow rate respectively were presented in Fig. 5a and b. It can be seen that the signal and the S/N of acetone and butanone increased gradually from 205 ◦ C to 250 ◦ C. This may be resulted from the higher catalytic activity of nanosized NaYF4 :Er (20%) at higher temperature. However, the experiment also indicated that the background signal, which mainly from the heat radiation, also increased rapidly even faster than the CTL intensity at higher temperatures. Considering signal and the S/N achieve maximum, therefore, the temperature of 250 ◦ C was selected as an optimum temperature in the subsequent experiments. The effect of the carrier flow rate on the CTL intensity of acetone and butanone were investigated in the air flow rate of 100–450 mL min−1 at the heating temperature of 250 ◦ C with a band pass filter of 490 nm. The results in Fig. 5c manifested CTL intensity of 23.88 ␮g mL−1 acetone increased gradually with the increase of air flow rate from 150 to 300 mL min−1 . When the air flow rate were 250 or 300 mL min−1 , the CTL intensity were the parallel but the S/N showed the very obvious difference and the S/N tended to be maximal at 250 mL min−1 . Fig. 5d indicated that CTL intensity and S/N of 24.50 ␮g mL−1 butanone on the NaYF4 :Er (20%) surface slowed down with the increase of the flow rate. It was similar to acetone and the higher air flow rate may lead to the reaction time between sample and catalyst not sufficient or the dilution of sample vapor, so that the sensitivity of the CTL detection system became lower. From these results, 250 mL min−1 and 100 mL min−1

were selected as optimal air flow rate for the identification of acetone and butanone gases, respectively. 3.5. Analytical characteristics Under optimal experimental conditions, the linearity and stability of the acetone and butanone sensor based on NaYF4 :Er (20%) were systematically studied. As shown in Fig. 6, a calibration curve for acetone and butanone with a linear range of 2.388–143.28 ␮g mL−1 and 2.45–49.0 ␮g mL−1 were obtained with a detection limit (S/N = 3) of 1.7 and 0.7 ␮g mL−1 , respectively. The linear regression equation of acetone was described by I = 487.190C − 780.226, and the butanone was I = 323.62C − 159.34 (correlation coefficient R = 0.99501 and 0.9938, where ‘R’ was the correlation coefficient). It has been reported previously that introduction of rare-earth elements into the catalyst would be favorable to the stability and sensitivity of the sensor [27]. The stability of sensor was determined by repeated extractions of 11.94 ␮g mL−1 acetone and 24.5 ␮g mL−1 butanone, respectively. The results presented in Fig. 7a and b, relative standard deviation (R.S.D, n = 5) were less than 3% and 5% respectively. 3.6. CTL response profiles of acetone and butanone on NaYF4 :Er (20%) The CTL response profiles on surface of NaYF4 :Er were investigated by continuous injecting acetone and butanone vapor of different concentrations under the optimal conditions. In Fig. 7c and

Fig. 4. (a) The effect of Er3+ -doping concentration on the CTL intensity. Conditions: wavelength, 490 nm; air flow rate, 250 mL min−1 and 100 mL min−1 , respectively, and temperature, 250 ◦ C. (b) FWHM of 28.24◦ peak vs. concentrations of Er3+ ions.


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Fig. 5. (a and c) The effect of temperature of acetone and butanone. Conditions: wavelength, 490 nm; air flow rate, 250 mL min−1 and 100 mL min−1 , respectively. (b and d) The effect of air carrier flow rate of acetone and butanone. Conditions: wavelength, 490 nm; temperature, 250 ◦ C. Error bars stand for ±S.D. (standard deviation).

d, it could be seen that the profiles of the CTL response were similar to each other. The fast response time of acetone and butanone were both short as 3 s, and the recovery time of acetone was less than 30 s, while the recovery time of butanone, which was about 60 s.

3.7. Selectivity of the CTL sensor Since a vapor could be detected only when it can be catalytically oxidized on the catalyst and at the same time the produced excited intermediates that fall back to ground states with light emission, a high selectivity CTL sensor was to be reasonably expected. To assess the selectivity of CTL sensor for ketones, the influences of some common foreign substances including acetonitrile, dipropylmethane, teriary butanol, methanol, methanoic acid,

propionaldehyde, methanal, acetaldehyde, ethanol, isopropanol and ethyl acetate were examined. In the present CTL sensor, the inspected species at a concentration of 73.5 ␮g mL−1 , which was nearly 3-fold times concentration than that of ketones, were injected individually at a carrier gas rate of 250 mL min−1 and temperature of 250 ◦ C at 490 nm. It is seen from Fig. 8 that only ketones including acetone, butanone, cyclohexanone, acetylacetonenone exhibited the significantly highest CTL intensity compared with all the foreign species. Except acetaldehyde, ethanol, isopropanol and ethyl acetate could give slight CTL responses; there were no CTL signal observed when acetonitrile, dipropylmethane, tertiary butanol, methanoic acid, propionaldehyde and methanol passed through the catalyst. The results have thus clearly illustrated the high selectivity of the NaYF4 :Er sensor for ketones.

Fig. 6. The calibration curve for acetone (a) and butanone (b) on NaYF4 :Er (20%) at optimal conditions.

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Fig. 7. CTL emissions from replicate injections of acetone (a) and butanone (b) on NaYF4 :Er (20%). (c and d) Typical CTL emission temporal profiles of acetone and butanone. (The profiles were smoothed by Origin software).

Analytical & Testing Center and College of Chemistry in Sichuan University. References

Fig. 8. Selectivity of ketones sensor. The concentration of interference of VOCs is 73.5 ␮g mL−1 and the concentrations of ketones are 26.2 ␮g mL−1 .

4. Conclusions In summary, a novel CTL gas sensor based on NaYF4 :Er nanocrystals was established for ketones. 20% Er3+ -doping concentration performed the higher CTL intensity at relatively low temperature. Meanwhile, this sensor exhibited excellent selectivity and rapid response as fast as 3 s. All of these excellent properties may pave the way to apply this sensor in environment and industry grounds. Acknowledgments The authors are grateful for the National Nature Science Foundation of China (no. 21375089 and 21105068) and the Fundamental Research funds for the Central Universities (2014SCU04A19),

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Biographies Jie Tang received her B.S. degree in 2011 from Chongqing Normal University, China. Now she is a Master candidate of analytical chemistry at Sichuan University, China. Her research interests are focused on synthesis of long afterglow phosphor material and application. Hongjie Song received her Ph.D. from Sichuan University in 2012. Now she is a faculty member in College of Chemistry at Sichuan University. Her current research is focused on nanomaterials-assisted chemiluminescence. BinRong Zeng received her B.S. degree in 2013 from Yangtze University, China. Now she is a Master candidate of analytical chemistry at Sichuan University. Her research interests are focused on synthesis of g-C3 N4 composite and their application in chemical sensor. Lichun Zhang received her Ph.D. from Sichuan University in 2010. Now she as a faculty member works at College of Chemistry in Sichuan University. Her areas of interest are the controllable synthesis of nanomaterials and their application in chemical sensor and biosensor. Yi Lv received his bachelor’s degree, master’s degree and Ph.D. degree from Southwest China Normal University (the current name is Southwest University) in 1997, 2000 and 2003, respectively. After a two-year stay in Tsinghua University as a postdoctoral fellow, he joined the faculty of the College of Chemistry at Sichuan University in 2005. His research interests are mainly in the areas of nanomaterials for analytical chemistry and luminescence-based sensors. He is the author or co-author of over 90 scientific publications in international journals and one book chapter.