Light-Regulated Electrochemical Sensor Array for Efficiently

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Light-regulated Electrochemical Sensor Array for Efficiently Discriminating Hazardous Gases Hongqiu Liang, Xin Zhang, Huihui Sun, Han Jin, Xiaowei Zhang, Qinghui Jin, Jie Zou, Hossam Haick, and Jiawen Jian ACS Sens., Just Accepted Manuscript • DOI: 10.1021/acssensors.7b00423 • Publication Date (Web): 01 Sep 2017 Downloaded from http://pubs.acs.org on September 1, 2017

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Light-regulated Electrochemical Sensor Array for Efficiently Discriminating Hazardous Gases

Hongqiu Liang†, Xin Zhang†,※, Huihui Sun‡, Han Jin†,※,*, Xiaowei Zhang$, Qinghui Jin$, ζ

, Jie Zou†, Hossam Haick†,§,£,*,and Jiawen Jian†,*

†

Gas Sensors & Sensing Tehcnology Lab, School of of Electrical Engineering and Computer Science, Ningbo University, Ningbo 315211, P. R. China

‡

Development Center of Qingdao National Laboatory for Marine Science and Technology, Qingdao, P. R. China

$

School of of Electrical Engineering and Computer Science, Ningbo University, Ningbo 315211, P. R. China

ζ

State Key Laboratory of Transducer Technology, Chinese Academy of Sciences, Shanghai

200050, P.R. China §

The Department of Chemical Engineering, and

£

The Russell Berrie Nanotechnology

Institute,Technion − Israel Institute of Technology, Haifa 3200003, Israel

Key words: Light-regulated electrochemical reaction; Gas sensor; Illumination; Discrimatinon features; PCA pattern recognition algorithm.

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Abstract Inadequate detection limit and unsatisfactory discrimination features remain the challenging issues for the widely applied electrochemical gas sensors. Quite recently, we confirmed that light-regulated electrochemical reaction significantly enhanced the electrocatalytic activity, thereby, can potentially extend the detection limit to parts per billion (ppb) level. Nevertheless, impact of the light-regulated electrochemical reaction on response selectivity is less discussed. Herein, we systematically report on the effect of illumination on discrimination features via designing & fabricating a light-regulated electrochemical sensor array. Upon illumination (light on), response signal to the examined gases (C3H6, NO and CO) is selectively enhanced, resulting in the sensor array demonstrates disparate response patterns when compared with that of the sensor array operated at light off. Through processing all the response patterns derived from both light on & off with pattern recognition algorithm, satisfactory discrimination feature is observed. In contrast, apparent mutual interference between NO and CO is found when solely operated the sensor array without illumination. Impact mechanism of the illumination is studied and it is deduced that effect of the illumination on the discriminating features can be mainly attribute to the competition of electrocatalytic activity & gas-phase reactivity. If the enhanced electrocatalytic activity (to specific gas) dominates the whole sensing progress, enhancements in the corresponded response signal would be observed when upon illumination. Otherwise, illumination gives negligible impact. Hence, response signal to part of the examined gases is selectively enhanced by illumination. Conclusively, light-regulated electrochemical reaction would providing an efficient approach to design future smart sensing devices.

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Electrochemical gas sensors have been potentially applied in variety of fields, such as the air quality monitoring1, 2, reducing exhaust gas emission3,

4

and potential

healthcare use5, 6, etc. This type of gas sensors that comes into many forms, e.g. yttria-stabilized zirconia(YSZ) based2 and nafion-based7, gains considerable attentions owing to their reliable performance, particularly in harsh conditions8. It has been reported that part of the electrochemical sensors can even continuously maintain satisfactory sensing performance under high humidity and high temperature (≥ 450oC) environment more than 1200 h9, which is rarely reported for other counterparts. However, inadequate detection limit (normally at dozen of parts per million, ppm level) and unsatisfactory selectivity still severely restrains their wide application2, 7, 8, 10. To date, several methods have been proposed to enhance the sensitivity & improve the detection limit which include but not limited to: introducing more electro-active sensing materials10, 11, 12, 13, fabricating a cascaded sensor array14 and increasing the reaction sites via etching the electrolyte15, 16. In contrast, improving the selectivity still mainly relays on finding appropriate sensing materials which is time consuming and inefficient10, 12, 13. At present, fabricating an electrochemical sensor array and operating it with the aids of compatible pattern recognition algorithm also provides potential way to obtain satisfactory discriminating features17. For the purpose of efficiently discriminating gas mixture, electrochemical sensor array is designed to consist of several sensor parts in which each sensor part is expected to be cross-sensitive to all the gases so that interference derived from other gas species can be easily eliminated with the help of pattern recognition algorithm17. Quite recently, the strategy based on the light-regulated electrochemical reaction has been proposed, offering an alternative approach extending the detection limit for the electrochemical sensors (e.g. YSZ-based gas sensor) to parts per billion (ppb) level6. Nevertheless, potential positive impact on the response selectivity that may be brought about by the light-regulated electrochemical reaction is less discussed. Theoretically, when upon illumination, considerable amount of some active gas species is expected to be converted to inactive products because of the significantly raised gas-phase reactivity (of the SE), leading to less amount of these gas species 3


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presenting the electrochemical reaction & generating minor corresponded response signal6. In other words, raised gas-phase reactivity would compensate the enhanced electrocatalytic activity. On the contrary, less active gas species will be partly converted, followed by triggering the illumination promoted electrochemical reaction and generating enhanced response magnitude, namely, the enhanced electrocatalytic activity dominates the whole sensing process. Based on this assumption, it is reasonable to deduce that disparate response patterns can be given by the same electrochemical sensor when sensing gas mixture simultaneously containing active & less active gas species without (light off) and with (light on) illumination. If processing all the response patterns (obtained at light off & on) with pattern recognition algorithm, discriminating features would be further improved, since more plentiful response patterns are expected. Herein, the vison and challenge of this research is to design and fabricate a light-regulated electrochemical senor array towards high-performance sensing of hazardous gases that mainly exist in the exhaust (e.g. CO, C3H6 and NO2). Impact of illumination on the discrimination capability will be explored and discussed to enrich our understanding of the mechanism, in particular, to clarify the practicability of providing an efficient approach designing future smart sensing devices via designing a light-regulated electrochemical sensor array. Experimental Sections The experimental details, including information of the full spectra LED lamp (Figure 1S of Supporting Information), materials synthesize and characterization, fabrication of the light-regulated electrochemical sensor array, sensing behavior measurements are all described in the Supporting Information. Results and discussion For the purpose of high-performance sensing C3H6, NO and CO (in the range of 15-100 ppm), a light-regulated electrochemical sensor array that comprised of several sensor parts (utilizing different photoactive SEs, such as the ZnO-18, ZnO/CeO2-19 and 4


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ZnO/Fe2O3-SEs20, Figure 1a) is designed and fabricated. Response patterns of the resultant sensor array that derived from each sensor part will be recorded with or without illumination (Figure 1b, c). Through processing all the response patterns with principal component analysis (PCA) pattern recognition algorithm, it is speculated that satisfactory discriminating features could be obtained if disparate response patterns are generated at light off & on (Figure 1d). Since, increased response magnitude is expected upon illumination, the resultant electrochemical sensor array should also demonstrate better sensing characteristics in its sensitivity and detection limit. (a)

(b)

(c)

(d)

Figure 1. Illustration of the light-regulated electrochemical sensor array and the overall experimental strategy: (a) schematics of the YSZ-based electrochemical sensor array comprised of several sensor parts that using different SEs (vs. Mn-based RE); (b) operating the electrochemical sensor array at light off & on and its sensing characteristics to C3H6, NO and CO is recorded; (c) response pattern derived from the sensor array operated at light off & on. It is expected that the recorded response patterns for each sensor part (upon illumination) is different with that of the sensor part operated at light off; (d) through processing all the expectant response patterns with the PCA algorithm, fully discriminated features that recorded in the from of PCA transformation is expected.

Initially, calcination and operational temperature for the sensor part utilizing ZnO-SE and Mn-based RE are optimized, and the related details can be found in Figures 3S, 4S of Supporting Information. In brevity, followed by calcined at 900oC & operated at 425oC, the illuminated sensor part (comprised of ZnO-SE) reaches its maximum response magnitude to all the examined gases. Based on these findings, the chemical composition and operational temperatures for the rest of the sensor 5


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parts comprised of ZnO/CeO2 and ZnO/Fe2O3 composites SEs are further optimized (shown in Figures 5S-7S and table 1S of Supporting Information). It can be confirmed that the optimum chemical composition for ZnO/CeO2 and ZnO/Fe2O3 composites electrodes is ZnO + 30 wt.% CeO2 and ZnO + 20 wt.% Fe2O3, respectively. Besides, 425oC is selected as the optimum operational temperature for all the sensor parts. As for the explanation of optimal calcination temperature at 900oC and the optimal sensing performance given by the chemical composition of ZnO + 30 wt.% CeO2 & ZnO + 20 wt.% Fe2O3, the following assumption is made based on the results shown in Figures 3S, 5S-7S and table 1S of Supporting Information: 1) the largest response magnitude that derived from the ZnO calcined at 900oC may probability due to: poor SE/YSZ interface that may result in low electrocatalytic activity is expected for the SE calcined at 800oC, while if the calcination temperature reaches 1000oC, particle size of the SE would will start to agglomerate significantly (decreasing the electrocatalytic & photocatalytic activity). Nevertheless, SE obtained at the calcination temperature of 900oC may demonstrate highest electrocatalytic & modest photocatalytic activity, thereby, revealing the optimal sensing behavior upon illumination. Further discussion can be found in our previous research6; 2) it has been confirmed that ZnO/CeO2 and ZnO/Fe2O3 are more photoactive than ZnO, CeO2 and Fe2O319,

20

, hence, the

increment in the reponse signal of the ZnO/CeO2 and ZnO/Fe2O3 composite electrode is apparently larger than that of the pure ZnO, CeO2 and Fe2O3 electrodes. Note that when the amount of CeO2 is more than 30 wt.%, it is assumed that part of the photoactive sites on the surface of ZnO were covered, consequently, declined the light-regulation effect if further increasing the amount of CeO2. Simlar explaination is expected for ZnO/Fe2O3 composite electrode, particularly, ZnO+20 wt.% Fe2O3 shows the highest surface area (table 1S of Supporting Information) so that the maximum photoactive sites may be given at the amount of 20 wt.% Fe2O3. Regarding to the phenomenon that the surface area decreased when the amount of Fe2O3 is more than 20 wt.%, this could be attributed to the formation of photo-inactive ZnFe2O4 which can be confirmed in Figure 5S. Then, an electrochemical sensor array comprised of these three sensor parts, 6


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i.e. sensor part consisting of ZnO-, ZnO + 30 wt.% CeO2- or ZnO + 20 wt.% Fe2O3-SE is fabricated. Figure 2a gives the photograph of the sensor array in which all the sensor parts share a Mn-based RE, its sensing behavior to C3H6, NO and CO in the range of 15-100 ppm can be seen in Figure 2b. Interestingly, in comparison with the sensing behavior recorded at light off, the sensor array shows the expectant disparate response patterns upon illumination. In order to give a more clear vision on the impact of illumination, sensing behavior recorded at light off and on is depicted in the form of heat map (Figure 2c) in which different color represents its corresponding sensing magnitude to specific gas. As it is expected that when the sensor array is illuminated, sensing response to the examined gases is selectively enhanced. For instance, the sensor part using ZnO-SE (operated at light on) reveals enhanced sensing response to all the examined gas species, while the enhanced performance for the sensor parts utilizing ZnO + 30 wt.% CeO2- and ZnO + 20 wt.% Fe2O3-SE is solely found for the gas species of (C3H6, CO) and C3H6, respectively. This conclusion can be further confirmed in Figures 3, 4 and table 1. In summary, beyond essentially improved sensitivity & detection limit (shown in Figures 3, 4 and table 1), the resultant sensor array gives 3 more response patterns when been illuminated (Figure 3). (a)

(b)

(c)

Figure 2. Photograph and sensing behavior of the electrochemical sensor array: (a) photograph of the sensor array; (b) sensing behavior of each sensor part in the sensor array to all the examined gases (in the rang of 15-100 ppm), operated at light off & on; (c) response patterns for the electrochemical sensor array depicted in the form of heat map. It can be seen that 3 more disparate response patterns are obtained when illuminating the sensor array. 7


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Figure 3. Response transients of the sensor array operated with or without illumination, toward 25 ppm C3H6, NO and CO.

Figure 4. Dependence of ∆V on the concentration of C3H6, NO and CO, in the range of 15–100 ppm for the sensor array operated at light off & on. In summary, illumination selectively enhanced the sensing magnitude of specific gas.

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Table 1. Sensing magnitude at 15 ppm, sensitivity and detection limit for the sensor array operated at light off & on, toward C3H6, NO and CO. Sensitivity and detection limit is obviously improved after illuminated the sensor array.

Sensing materials

ZnO

ZnO + 30 wt.% CeO2

ZnO + 20 wt.% Fe2O3

Target gas C3H6 NO CO C3H6 NO CO C3H6 NO CO

-∆V (at 15 ppm) / mV light off light on 30.12 43.15 16.11 22.42 15.21 16.32 38.14 48.0 2.85 2.89 4.94 8.16 101.79 106.14 3.05 3.11 12.64 12.64

Sensitivity / (mV/Dec.) light off light on -43.17 -47.66 -4.22 -4.97 -17.06 -29.38 -23.81 -25.28 -1.44 -1.49 -23.48 -30.03 -40.50 -41.69 -2.77 -2.92 -22.11 -22.15

(a)

(b)

(c)

(d)

Detection limit / ppm light off light on 3.79 1.98 5.75 3.17 5.97 3.84 2.98 1.01 14.9 14.3 12.1 5.37 0.857 0.751 14.7 14.0 4.57 4.57

Figure 5. PCA transformation of the data set for the light-regulated electrochemical sensor array: PCA transformation generated by processing (a) 3 response patterns derived from the sensor array (comprised of 3 sensor parts) solely operated at light off; (b) 6 disparate response patterns derived from the sensor array (comprised of 3 sensor parts) operated at light off & on; (c) 2 response patterns derived from the sensor array (comprised of 2 sensor 9


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parts) solely operated at light off; (d) 4 response patterns derived from the sensor array (comprised of 2 sensor parts) solely operated at light off and on. Discrimination feature derived from the sensor array operated at light off & on is remarkably improved. Besides, the evidence of the minimal and optimal combinations for the sensor array without sacrificing its performance indicates the bright future of producing a low power & compact sensor array.

Since 3 more response patterns are obtained by simply exposed to illumination, a better discrimination feature is expected when compared with that of the sensor array solely operated at light off. To confirm this speculation, PCA transformation is depicted via processing all the 6 response patterns (i.e. 3 obtained at light off, 3 obtained at light on) with the PCA algorithm. A feature vector of 15 ×6 (row ×column) consisting of response patterns to these hazardous gases in the range of 15-100 ppm is created as the input to PCA. Note that the same colored symbol within the PCA transformation corresponds to specific gas and a large spatial distance between these symbols suggests a desirable discrimination feature given by the sensor array. The PCA transformation shown in Figure 5a derives from the sensor array operated without illumination (i.e. by solely input 3 response patterns). Obvious overlap is witnessed for the PCA transformation of CO and NO, suggesting serious mutual interference if utilizing the sensor array (operated at light off) sensing the gas mixture. In contrast, satisfactory discrimination feature (Figure 5b) is generated by input 6 response patterns that derived from the sensor array operated with & without illumination. In other words, all the examined gases can be artificially classified with high selectivity. Figures 5c, d and 8S-10S of Supporting Information show the PCA transformation comes from different combination of these 3 sensor parts. It is interesting to find that acceptable discrimination feature (Figure 5c, d) can be even obtained by design a sensor array comprised of 2 sensor parts in which consisting of ZnO- and ZnO + 30 wt.% CeO2–SEs (vs. Mn-based RE) with the aids of illumination, implying the number of sensor parts in the sensor array can be further reduced while keeps the high performance. These interesting & promising results indicate the light-regulated electrochemical reaction could indeed provide an efficient approach for designing next generation low power & compact smart sensing devices with enhanced sensitivity and 10


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detection limit, particularly, promoted discrimination capability.

Sensing materials

ZnO

ZnO+ 30 wt.% CeO2

ZnO + 20 wt.% Fe2O3

Target gas C3H6 NO CO C3H6 NO CO C3H6 NO CO

(C1) Conversion of target gas at 425oC without illumination

(C2) Conversion of target gas at 425oC with illumination

∆C=C2-C1

9.7% 5.1% 5.1%

12.3% 8.4% 6.6%

2.6% 3.1% 1.5%

15.6% 19.2% 10.3%

19.7% 28.5% 14.5%

4.1% 9.3% 4.2%

18.7% 13.2% 12.8%

20.5% 18.6% 18.9%

1.8% 5.4% 6.1%

Table 2. Conversion percentage of target gas at light on (and off) for the ZnO, ZnO/CeO2 and ZnO/Fe2O3 composites powder.

Figure 6. Schema for the impact mechanism of illumination on the response patterns. When SE demonstrates modest gas-phase reactivity upon illumination, target gas (e.g. CO) will be converted to intermediates on the surface of SE, followed by presenting electrochemical reaction at the SE/YSZ reaction interface and generating corresponded response signal. Due to the enhanced electrocatalytic activity by illumination, response signal is raised, resulting in a higher sensing performance. In contrast, if the SE gives extremely high gas-phase reactivity & electrocatalytic activity when be illuminated, the conversion rate of target gas (e.g. CO) at the surface of SE will be notably increased, leading to less amount of target gas reaching the reaction interface, this would decrease the response signal. However, owing to the significantly enhanced electrocatalytic activity, the negative effect (in the response 11


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signal) caused by the raised gas-phase reactivity will be compensated, therefore, illumination gives minor impact on the sensing behavior6.

To understand and clarify the impact mechanism of illumination, gas-phase & photocatalytic activity of each SE at light off & on is examined. Table 2 summarizes the comparison for ZnO, ZnO + 30 wt.% CeO2 and ZnO + 30 wt.% Fe2O3, and the impact mechanism on the response patterns is depicted & described in Figure 6 & equations (Eqs.) 1-13. Brevity, ZnO + 30 wt.% CeO2 and ZnO + 30 wt.% Fe2O3 exhibit relatively high photocatalytic activity & gas-phase reactivity to NO and (NO & CO), respectively. This may result in the enhanced electrocatalytic activity (to the corresponded gas species) compensated by the negative effect that derived from the remarkably raised gas-phase reactivity (as shown in eqs.1-6, 7-9)6. Accordingly, illumination gives negligible impact on the sensing performance of the sensor parts comprised of ZnO + 30 wt.% CeO2- (to NO) and ZnO + 30 wt.% Fe2O3 (to NO & CO)-SEs. Regarding to the enhancements observed for the response of the sensor parts utilizing ZnO- (to C3H6, NO and CO), ZnO + 30 wt.% CeO2 (to C3H6 and CO) and ZnO + 30 wt.% Fe2O3 (to C3H6)-SEs, this can be explained through their modest photocatalytic activity & gas-phase reactivity to the corresponded gas species, in which the enhancement in electrocatalytic activity (to the corresponded gas species) may dominate the whole sensing progress and lead to the enhanced sensing signal when illuminated. Since, the illumination solely enhances the response signal to part of gas components, disparate response patterns are obtained when illuminating the sensor array. Conclusively, owing to the competition of electrocatalytic activity & gas-phase reactivity of the electrochemical sensor, illumination can selectively (even exclusively) increase the sensing signal to specific gas and is helpful to promote the discrimination capability.

i When upon illumination: a. Gas phase reaction (upon illumination, gas-phase reactivity increased. This will significantly decrease gas amount that can reach the reaction interface and is adverse to generate adequate sensing signal): 12


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Photoactive SE (e.g. ZnO) +hv →e-(hv)+ h+(hv)

(1)

O2 + e-(hv)→O-(hv)

(2)

Target gas (e.g. CO) + h+(hv)→ Intermediates (Intermed.)

(3)

or Target gas (e.g. CO) + O-(hv)→ Intermediates (Intermed.) (4) b. Electrochemical reaction (upon illumination, the electrocatalytic activity is essentially enhanced. Since the electrochemical reaction directly determine the generated sensing signal, the enhanced electrocatalytic activity is helpful to increase the response signal): O-(hv) + e-→O2-

(5)

Intermediates+ O2-→CO2 + 2e-

(6)

iI. When operated at light off: a. Gas phase reaction: 2C3H6 + 9O2→6CO2 + 6H2O

(7)

2NO + O2→ 2NO2

(8)

2CO + O2→2CO2

(9)

b. Electrochemical reaction: O2 + 4e-→2O2-

(10)

C3H6 + 9O2-→3CO2 + 3H2O + 18e-

(11)

NO + O2-→ NO2 + 2e-

(12)

CO + O2-→CO2 + 2e-

(13)

Summary and Conclusions Intending to efficiently discriminating hazardous gas, a light-regulated electrochemical sensor array which comprised of 3 photosensitive sensor parts is designed and fabricated. Impact of illumination on the discrimination features of the sensor array is thoroughly studied. Typically, sensing response of the sensor array (upon illumination) is selectively enhanced to specific gases, leading to generating disparate response patterns when compared that of the sensor array operated without illumination. Hence, after processing all the response patterns (derived from light off & on) with PCA algorithm, the discrimination capability for the sensor array is further improved. The 13


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impact mechanism of illumination is studied, it is deduced that effect of the illumination on the discriminating features can be attribute to the competition of photocatalytic activity & gas-phase reactivity. In conclusion, benefiting from the greatly improved sensitivity, detection limit and promoted discriminating capability, we anticipate that this light-regulated electrochemical reaction will be a starting point for future designing of smarter sensing devices. Note that since the minimal operating temperature for YSZ-based gas sensor is 400oC which is inconvenient for most of the real application, electrolytes that can be operated at room temperature, e.g. Nafion-based electrolyte will be considered to replace the used zirconia-based electrolyte in future research. Additionally, in consideration of the fact that sunlight will potentially affect the performance of the sensor when used in real world ambient conditions, it is better to encapsulate a mini LED lamp with the sensor for providing extra light and

eliminate any potential interference from sunlight.

Associated Content: Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. Experimental details related to information of the full spectra LED lamp, materials synthesize and characterization, fabrication of the light-regulated electrochemical sensor array and sensing behavior measurement; Figure 1S: Web link and photograph of the full spectra LED lamp (eBay); Figure 2S: Schematics of apparatus for evaluating the gas-phase reactivity &

photocatalytic activity of the ZnO, ZnO/CeO2 and ZnO/Fe2O3 powers; Figure 3S: Response o

magnitude to 15 ppm C3H6 for the sensor part using ZnO-SE (calcined at 800-1000 C, with the o

o

intervals of 200 C) and Mn-based RE, operated at 450 C, with (light on) and without illumination (light off); Figure 4S: Response transients to C3H6, NO and CO (in the range of o

15-25 ppm) for the sensor part using ZnO-SE (calcined at 900 C) vs. Mn-based RE, operated o

at the temperature of 400-500 C, with or without illumination; Figure 5S: Response magnitude to 25 ppm C3H6 for the sensor parts comprised of binary ZnO-based composite SEs vs. Mn-based RE, in which the amount of additives varies in the range of 5-40 wt.%; Figure 6S: XRD patterns for (a) ZnO/CeO2 and (b) ZnO/Fe2O3 composites, with the amount of additives varies in the range of 5-40 wt.%; Figure 7S: Response magnitude of the sensor parts comprised of ZnO+ 30 wt.% CeO2- and ZnO+20 wt.% Fe2O3-SEs vs. Mn-based RE, operated o

at the temperature of 400-500 C; Figure 8S: PCA transformation of the sensor part utilizing 14


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ZnO-SE (vs. Mn-based RE), operated at light off and on ; Figure 9S: PCA transformation of the sensor array utilizing ZnO -, ZnO+20 wt.% Fe2O3-SEs (vs. Mn-based RE), operated at light off and on; Figure 10S: PCA transformation of the sensor array utilizing ZnO+30 wt.% CeO2-, ZnO+20 wt. % Fe2O3-SEs (vs. Mn-based RE), operated at light off and on. Table 1S: Specific surface area of the ZnO, CeO2 and Fe2O3, as well as their corresponded ZnO-based o

composites, after calcined at 900 C for 2.5 h.

Corresponding Authors * H. Jin. Email: [email protected] * H. Haick. Email: [email protected] * J. W. Jian. Email: [email protected] ※

These authors contributed equally to this work

Acknowledgments The authors gratefully acknowledge the financial support for this research from Research Award Found (ZX2017000001), K. C. Wong Magna Fund in Ningbo University, Natural Science Foundation of Ningbo City (2017A610229) and National Natural Science Foundation of China (61771267, 61301050, 61601253, 5161556 and), as well as the Scientific Research Grant supported by Enterprise (Grant ID: ZX2016000638, ZX201600068076).

Competing financial interests The authors declare no competing financial interests.

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