Journal Pre-proofs

Enhanced benzene sensing property of Au-Pd@ZnO and Au-Pt@ZnO core-

shell nanoparticles: the function of Pt/Pd decorated Au-ZnO hetero-interface

Min Yang, Yan Gong, Genli Shen, Zhen Wang, Mi Liu, Qi Wang

PII: S0167-577X(20)31440-3
DOI: https://doi.org/10.1016/j.matlet.2020.128733
Reference: MLBLUE 128733

To appear in: Materials Letters

Received Date: 20 July 2020

Revised Date: 27 August 2020
Accepted Date: 21 September 2020

Please cite this article as: M. Yang, Y. Gong, G. Shen, Z. Wang, M. Liu, Q. Wang, Enhanced benzene sensing
property of Au-Pd@ZnO and Au-Pt@ZnO core-shell nanoparticles: the function of Pt/Pd decorated Au-ZnO
hetero-interface, Materials Letters (2020), doi: https://doi.org/10.1016/j.matlet.2020.128733

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Enhanced benzene sensing property of Au-Pd@ZnO and Au-Pt@ZnO core-shell

nanoparticles: the function of Pt/Pd decorated Au-ZnO hetero-interface

Min Yanga,+, Yan Gongb,+, Genli Shenb, Zhen Wangb, Mi Liub,* and Qi Wangb,*
a Department of Chemistry, School of Chemistry and Biological Engineering,
University of Science and Technology, Beijing 100083, China
b CAS Key Laboratory of Standardization and Measurement for Nanotechnology,
CAS Center for Excellence in Nanaoscience, National Center for Nanoscience and Technology,
Beijing 100190, China
* Corresponding author: liumi@nanoctr.cn; wangq@nanoctr.cn
+ These authors contributed equally to this work and should be considered co-first authors

Abstract

Core-shell Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO nanoparticles were synthesized, aiming at figuring

out the function of Au-ZnO hetero-interfaces. Pd/Pt was decorated on Au cores which were confirmed

by using various techniques. The optimal operating temperature of all synthesized core-shell NPs based

sensors (300°C) is much lower than ZnO NPs (400°C). By comparing gas sensing properties towards

ppb-ppm level benzene, the Au-Pd@ZnO and Au-Pt@ZnO nanoparticles had better benzene sensing

property than Au@ZnO nanoparticles. The Pt/Pd decorated Au-ZnO hetero-interface had positive

influence on benzene sensing performance, because decoration of Pt and Pd further enhanced electron

transfer phenomenon on Au-ZnO hetero-interfaces which was advantageous on benzene sensing property.

Key words: hetero-interface, core-shell, nanoparticles, benzene, sensors

Introduction

Benzene (C6H6) is a highly poisonous toxin and hard to detect, there are urgent requirements for real-

time and high sensitivity benzene-sensor. Zinc oxide (ZnO) based sensors are one of the most promising

candidates due to advantages such as good semiconducting nature, high stability, low cost, easy-achieved

and real-time response [1]. However, there are some obstacles to detect trace levels gas for ZnO-based

materials, such as unsatisfactory sensitivity, poor selectivity and signal drifts [2]. The core-shell structure

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is an important technique for surface modification which can restrain particles from congregate together,

and it is also an important research branch in gas-sensing area [3]. Heterojunction-depletion plays an

important role in gas-sensing mechanism of core-shell nanoparticles, but there lacks empirical data and

deep theoretical insights about it. Hence, it is important to find out the relationship between hetero-

interfaces and gas sensing property.

In this work, we try to manipulate the electrical properties of Au-ZnO hetero-interface which may lead

to change of sensing performance. Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO core-shell nanoparticles

were synthesized. The trace level of benzene sensing performances of the synthetic samples was assessed,

the function of Pt/Pd decorated Au-ZnO hetero-interfaces were analyzed and discussed.

Experimental section

Au nanoparticles were prepared by wet chemical method [4] and Pd and Pt decorated Au NPs were

prepared by chemical reduction, detail synthetic method was listed in Supplementary Material. The core-

shell NPs were synthesized according to our previous report [5]. First, 131.2 mg of

Hexadecyltrimethylammonium bromide (CTAB) ,31.7 mg of L-ascorbic acid (AA), 54.5 mg of

Hexamethylenetetramine (HMT), 107.1 mg of zinc nitrate hexahydrate (Zn(NO3)2·6H2O) and as-

prepared noble NPs solution (the molar ratio of Zn/Au is 40/1) were dissolved evenly in deionized 60

mL water. The resulting solution was kept in sealed glass bottle at 85°C for 8 h. Then, the collected liquid

was centrifuged and washed by water and alcohol for 3 times and dried at 60°C for 6 h. Finally, the dried

powders were sintered at 500°C (ramp of 2°C·min-1) for 2 h. ZnO NPs was synthesized following the

same approach without noble NPs. The gas sensing measurements were performed by a computer

controlled gas-detecting system [6], detail measurement method were listed in Supplementary Material.

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Results and discussion

The nanostructures are analyzed by Scanning TEM (STEM) coupled with energy dispersive X-ray

spectroscopy (EDX) to confirm the Pt/Pd decorated Au NPs. TEM images of Au NPs is about 35 nm

(Fig. 1a), the Au@ZnO is about 220 nm after hydrothermal process (Fig. 1b). After calcining process,

the particles become about 120 nm (Fig. 1c). Surface morphology of Pt decorated Au NPs (Fig. 1d)

become rough and the particle diameter is hardly changed. Pd decorated Au NPs (Fig. 1e) surface

morphology seem smooth which means Pd is evenly distributed. The geometrical lattice matching theory

can explain this phenomenon, due to the similar work function between Au and Pd (5.65 eV for Pt, 5.12

eV for Pd, 5.10 eV for Au). Pt-Au@ZnO and Pd-Au@ZnO samples have similar shape and size with

Au@ZnO sample. According to Fig 1c, 1f and 1j, the grain size of the Pt-Au@ZnO and Pd-Au@ZnO

shells becomes larger (from about 15nm to 25 nm). The SEM images of all core-shell NPs are displayed

in Fig. S1, the EDS results are shown in Fig. S2 which indicating the Pt/Pd are decorated on Au NPs.

The XRD patterns of all NPs are shown in Fig. 2a Characteristic diffraction peaks of cubic Au (JSPDS.

No. 01-089-3697) ZnO (JSPDS. No. 01-080-0075) can be detected from all core-shell NPs. There are no

peaks of Pt and Pd. Because the additive content of Pt and Pd is low and there is some overlap at the

characteristic diffraction peaks of Au, Pt and Pd. Moreover, according to Debye-Scherrer Equation [12],

the calculated ZnO grain size of Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO NPs is 15 nm, 24 nm and 25

nm which is consistent with TEM.

Fig. 2b presents the UV spectroscopy of three noble NPs. Au NPs display a peak at 536 nm attributing

to surface plasmatic resonance (SPR) [7]. Because of the illegible SPR signal of metallic Pd/Pt [8] and

the low additive content of Pt/Pd, there are no SPR peaks of the Pd/Pt detected. Blue-shift of Au-Pt and

Au-Pd NPs are observed at 528 and 534 nm, indicating decoration of Pt and Pd could increase the

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electronic concentration of Au NPs. Fig. 2c presents the UV spectroscopy of core-shell NPs. Au@ZnO

displays a wide peak at 628 nm attributing to SPR of Au cores. Compared to Fig 2b, this remarkable red-

shift is caused by increasing of steric hindrance [9], due to encapsulation of the ZnO. There are no Au

SPR responses of the Au-Pd@ZnO and Au-Pt@ZnO, which is due to Pd/Pt covered on Au cores. The

peaks of ZnO which belong to ZnO, Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO NPs are at 374 nm, 381,

378 and 383 nm. For Au@ZnO NPs, the red-shift means that the outer electrons are dragged from the

ZnO shells to noble cores, and decoration of Pt/Pd further enhances electron transfer phenomenon.

According to Fig. 2b, Pt decorated Au NPs have higher electronic concentration, but the red-shift of ZnO

in Au-Pd@ZnO NPs are more pronounced. Because Pd is more evenly distributed on Au NPs which is

advantageous for electron transfer on Au-ZnO hetero-interface.

To evaluate the gas sensing property, all NPs were applied to detect low concentration (ppb~ppm)

benzene. Operating temperature is a key factor for gas sensors [10], Fig 3a displays the relationship

between sensing response and operating temperature towards 1 ppm benzene at 200~400°C. The optimal

operating temperature of all core-shell NPs based sensors (300°C) is much lower than ZnO NPs (400°C).

Fig. S3a displays the sensing responses of all NPs towards 0.1 to 5 ppm benzene. And the sensitivity

sequence of those sensors towards benzene is Au-Pd@ZnO > Au-Pt@ZnO > Au@ZnO > ZnO, which is

well consistent with the red-shift of ZnO UV adsorption peaks in Fig. 2c. Fig. 3b shows the dynamic

response-recovery curves of all core-shell NPs based sensors towards 1 ppm benzene. The sensing

response of Au-Pd@ZnO sensor towards 1 ppm benzene is 2 times higher than Au@ZnO (0.27 vs. 0.12)

and 1.8 times higher than Au-Pt@ZnO (0.27 vs. 0.15). Among various gases (such as 1 ppm acetone,

ethanol, benzene and toluene), Au-Pd@ZnO sensor demonstrates good selectivity towards benzene (Fig.

3c). Fig. 3d and 3e displays the dynamic resistance curves of Au-Pd@ZnO based sensor towards 0.1-5

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ppm and 10-80 ppb benzene. The dynamic resistance curves of Au@ZnO and Au-Pt@ZnO based sensor

towards 0.1-5 ppm benzene are listed in Fig. S3b and S3c. The detect limit of Au-Pd@ZnO based sensor

is 10 ppb, and ZnO, Au@ZnO and Au-Pt@ZnO NPs based sensors show no response towards 50 ppb

benzene or below. Good stability performance of Au-Pd@ZnO sensor for 1 ppm benzene and at operating

temperature of 300°C is displayed in Fig. 3f.

Modulation model of surface electron depletion layer is the generally accepted sensing mechanism for

n-type semiconductor gas sensors such as ZnO [11]. In this work, the Au-ZnO Schottky junction induces

the redistribution of excited electrons at Au-ZnO hetero-interfaces, due to the work function difference

(5.10 eV for Au, 4.65 eV for ZnO). Consequently, excited electrons are transferred from ZnO to Au core

which leads to electronic concentration reducing on ZnO shells. The electronic concentration reducing

of ZnO shells enhances the adsorption capacity for absorbing active chemisorbed oxygen which also

enhances the sensing performance [5, 6]. Moreover, decoration of Pd/Pt enhances the redistribution of

excited electrons at the Au-ZnO hetero-interfaces, due to the work function differences (5.65 eV for Pt,

5.12 eV for Pd, 5.10 eV for Au), which would further enhance the sensing performance of Au-Pd@ZnO

and Au-Pt@ZnO.

Conclusions

Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO core-shell nanoparticles were synthesized through

hydrothermal reaction and calcining treatment. The Au-ZnO Schottky junction inside the core-shell

Au@ZnO NPs induces the redistribution of excited electrons at the Au-ZnO hetero-interfaces which

enhances the sensing performance of core-shell Au@ZnO NPs. The optimal operating temperature of all

core-shell NPs based sensors (300°C) is much lower than ZnO NPs (400°C). By comparing gas sensing

properties towards ppb-ppm level benzene at 300°C, the Au-Pd@ZnO and Au-Pt@ZnO nanoparticles

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had better benzene sensing property than Au@ZnO nanoparticles. Decoration of Pd/Pt enhances the

redistribution of excited electrons at the Au-ZnO hetero-interfaces, due to the work function differences

(5.65 eV for Pt, 5.12 eV for Pd, 5.10 eV for Au), which would further enhance the benzene sensing

performance of Au-Pd@ZnO and Au-Pt@ZnO.

Acknowledgments

This work was financially supported by the Basic Research Foundation of University of Science and

Technology Beijing (No. FRF-BR-18-001A).

References

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[9] Singh S, Tripathi P, Kumar N, Nara S. Biosens Bioelectron 2017; 92: 280–6.

[10] Zhou X, Feng W, Wang C, Hu XL, Li XW, et al. J Mater Chem.A 2014; 2: 17683–90.

[11] Xu JQ, Pan QY, Shun YA, Tian ZZ, Sensor Actuat B-Chem 2000; 66: 277–9.

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Fig. 1 TEM images of Au seed NPs and Au@ZnO NPs (a, b and c); Au-Pt seed NPs and Au-Pt@ZnO

NPs (d, e and f); Au-Pd seed NPs and Au-Pd @ZnO NPs (g, h and i)

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Fig.2 XRD patterns of Au@ZnO, Au-Pd@ZnO and Au-Pt@ZnO NPs (a); UV-visible spectra of nobel

NPs (b) and core-shell Metal@ZnO NPs (c)

Fig. 3 The relationship between sensing response and operating temperature towards 1 ppm benzene

(a); The dynamic response-recovery curve of the Au@ZnO, Au-Pt@ZnO and Au-Pd@ZnO towards 1

ppm benzene (b); selectivity performance of different at 300°C (c); the dynamic resistance curves of

Au-Pd@ZnO based sensor towards 0.1-5 ppm (d) and 10-80 ppb benzene at 300°C (e); stability

performance of Au-Pd@ZnO sensor

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 CRediT authorship contribution statement

Min Yang: Methodology, Writing-original draft. Yan Gong: Methodology, Validation, Writing-

original draft. Genli Shen: Visualization. Zhen Wang: Writing-review & editing. Mi Liu:

Conceptualization, Resources, Supervision. Qi Wang: Methodology, Validation, Writing-original

draft.

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Highlights

Benzene sensing performance was evaluated for synthesized core-shell nanoparticles.

Au-Pd@ZnO and Au-Pt@ZnO sensors had enhanced benzene sensing performance.

Work function differences caused excited electrons redistribution at hetero-interfaces.

Decoration of Pd/Pt enhances the electron transfer phenomenon at hetero-interfaces.

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