Mechanochemical Synthesis of Defective Molybdenum Trioxide

Research Article pubs.acs.org/journal/ascecg

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Mechanochemical Synthesis of Defective Molybdenum Trioxide, Titanium Dioxide, and Zinc Oxide at Room Temperature Rui Li,†,‡ Jinhu Wang,† Yi He,*,† Faqin Dong,*,‡ Liang Bian,‡ and Bowen Li§ †

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State Key Laboratory of Environment-friendly Energy Materials, Sichuan Co-Innovation Center for New Energetic Materials, School of National Defense Science & Technology, Southwest University of Science and Technology, Mianyang 621010, P. R. China ‡ China Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education, State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, Southwest University of Science and Technology, Mianyang 621010, P. R. China § Department of Materials Science and Engineering, Michigan Technological University, Houghton 49931, United States S Supporting Information *

ABSTRACT: Defect engineering on metal oxide semiconductors is considered as a versatile approach to regulate their properties. The traditional method for preparation of defective metal oxide semiconductors always requires harsh reaction conditions such as high temperature, high pressure, and explosive chemicals. Here we report an environmentally friendly mechanochemical synthesis way for preparation of several defective metal oxide semiconductors (MoO3, TiO2, and ZnO) in 10 g quantities by grinding semiconductor powders with ascorbic acid. The resulting vacancy-rich TiO2 and ZnO show a strong visible-light absorption. Meanwhile, the obtained hydrogendoped MoO3 (H0.5MoO3) exhibits an exceptional localized surface plasmon resonance (LSPR), which follows Prout-Tompkins B1 solid-state reaction model. In addition, the plasmonic H0.5MoO3 is further utilized for colorimetric detection of H2O2. This colorimetric assay is able to determine concentrations of H2O2 from 0.05 to 3 mM with a detection limit of 30 μM. It can distinguish the presence of 3 mM H2O2 by the naked eye. KEYWORDS: Mechanochemical synthesis, Defect, Localized surface plasmon resonance, Colorimetry, Hydrogen peroxide

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INTRODUCTION Defect engineering in metal oxide semiconductors has been demonstrated as an effective route to tune their performances, because the defect structures of metal oxide semiconductors strongly affect their fundamental chemical and physical properties as well as practical applications.1−15 For instance, molybdenum trioxide (MoO3), a stable n-type metal oxide semiconductor with a bandgap of 3.2 eV, can show metallic behavior when the detects such as hydrogen doping are introduced because of the increase of free carrier concentration.16−20 As a result, the defective MoO3 exhibits localized surface plasmon resonance (LSPR) which are widely investigated in noble metal nanomaterials.21,22 Additionally, the introduction of vacancy-oxygen defects into TiO2 is able to enhance its visible light absorption as well as photocatalytic activity.23 To date, several approaches have been developed to prepare defective MoO3, TiO2, and ZnO. Recently, Yamashita’s group reported an H-spillover route to prepare hydrogen doped MoO3 with strong LSRP property by Pd catalytic hydrogenation at 300 °C for 2 h.24 Zhang et al. developed a hydrothermal method for synthesis HxMoO3 at 180 °C for 3 h using tartaric acid as the reducing agent.25 However, these methods involve harsh reaction conditions, © XXXX American Chemical Society

including high temperature, high pressure, and explosive chemicals. As an alternative to traditional chemical preparation in solution, mechanochemical synthesis by grinding or milling has emerged as an environmentally friendly approach. It offers cleaner, more efficient, faster, and solvent-free reaction environment for a variety of transformations, including drug cocrystals, nanomaterials, metal−organic frameworks, covalent organic frameworks, metal nitrides, and metathesis.26−30 Despite its popularity and wide application, mechanochemical synthesis of defective MoO3, TiO2, and ZnO is not reported in the literature to the best of our knowledge. Herein, we develop a simple, effective, rapid, scalable method for synthesis of defective metal oxide semiconductors in gram quantities by directly grinding semiconductor powders with ascorbic acid (Figure 1). Several metal oxide semiconductors, including MoO3, TiO2, and ZnO, are doped with hydrogen atoms or oxygen vacancies. Besides, the resulting hydrogen doped MoO3 shows exceptional LSPR, which is Received: January 21, 2019 Revised: April 11, 2019

A

DOI: 10.1021/acssuschemeng.9b00374 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Figure 1. Schematic of the mechanochemical synthesis of defective metal oxide semiconductors.

applied to visually determine hydrogen peroxide. And the oxygen vacancy-rich TiO2, and ZnO display an optical absorption characteristic in the visible-light region.

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Figure 2. Pristine and defective metal oxide semiconductors. (a) Photographs and XRD patterns of pristine and defective (b) MoO3, (c) TiO2, and (d) ZnO.

EXPERIMENTAL SECTION

Chemicals. MoO3 powder, hydrogen peroxide, and inorganic salts were purchased from ChengDu KeLong Co., Ltd. TiO2 nanopowder, ZnO powder, L-ascorbic acid, L-glutathione, L-cysteine hydrochloride monohydrate, D-glucose, and α-lactose monohydrate were obtained from Aladdin Chemical Co., Ltd. All of the chemicals were used as received without further purification. The deionized water (DI, 18.2 MΩ·cm) was used to prepare various solutions. Synthesis of Defective Metal Oxide Semiconductors. A total of 10 g of metal oxide semiconductors and a certain amount of Lascorbic acid as the reducing agents were put in a mortar, followed by grinding for 1 h using a pestle at room temperature. The resulting powders were dispersed into DI water. After centrifuging and washing with DI water, the resulting defective metal oxide semiconductor was dried at room temperature for further characterization. Procedure of Colorimetric Detection of H2O2. Typically, a series of 2.3 mL H2O2 solutions with different concentrations were added to several 5 mL glass vials. Subsequently, 0.7 mL of hydrogen doped MoO3 (H0.5MoO3) dispersion was injected to each vial. After 10 min incubation at room temperature, the UV−vis absorption and the corresponding photographs were collected by UV−vis spectrometer and camera, respectively. Characterization. UV−vis absorption spectra were obtained from absorption spectrophotometer (UV-1800, Shimadzu). Scanning electron microscope (SEM) images were recorded with MAIA3LMU scanning electron microscopy (TESCAN). X-ray diffraction (XRD) patterns were taken on an X Pert pro X-ray diffractometer. X-ray photoelectron spectroscopy (XPS) spectra were carried out performed on a Thermo Escalab 250Xi spectrophotometer. Fourier transform infrared (FTIR) spectra were conducted on a TENSOR spectrophotometer (Bruker).

(Figure 2b). It can be seen that the resulting H0.5MoO3 only shows few XRD peaks. The reason is that the interaction between water and H0.5MoO3 induces the exfoliation of H0.5MoO3 to generate two-dimensional H0.5MoO3 nanosheet, which damages the three-dimensional structure of H0.5MoO3 during the dissolution process for separation and purification, leading to the disappearance of the diffraction peaks from three-dimensional diffraction lines (Figure S1). In order to prove the generality of this mechanochemical synthesis method, we employ the same strategy to synthesize defective TiO2 and ZnO. Similarly, the distinct color changes from white to yellow are observed in the ascorbic acid-treated TiO2 and ZnO (Figure 2a). As displayed in Figure 2c,d, the XRD patterns of TiO2 and ZnO after reaction do not change, demonstrating that the mechanochemical reaction does not alter their intrinsic crystal structures. Accordingly, the color change is ascribed to be the fact that the TiO2 and ZnO are able to be partially reduced to generate oxygen vacancy-rich TiO2 and ZnO (TiO2‑x and ZnO1−x), which increases the visible light absorption.31,32 Meanwhile, this mechanochemical synthesis approach is easily used for scalable preparation of defective metal oxide semiconductors in ten-gram quantities as shown in Figure S2. The morphology of MoO3 and H0.5MoO3 is investigated by SEM. As depicted in Figure 3a, the MoO3 have microsized plates. When it is transformed into H0.5MoO3, the layer structure is well preserved (Figure 3b), implying successful hydrogen doping without breaking the inherent structure. To confirm the doping of hydrogen into MoO3, we perform XPS measurements as presented in Figure 3c,d. The high-resolution Mo 3d XPS spectra of MoO3 reveals two characteristic binding energy peaks at 233.3 and 236.4 eV, originating from 3d5/2 and 3d3/2 of Mo6+ species (Figure 3c).32,34 Hydrogen doping causes the Mo 3d XPS spectra to broaden, which can be fitted into a set of doublet peaks (Figure 3d). Except for Mo6+, two peaks at 232.2 and 234.8 eV corresponding to 3d5/2 and 3d3/2 of Mo5+ are found, indicating that the hydrogen doping induces the partial reduction of MoO3. Also, the morphology, structure, and surface composition of TiO2‑x and ZnO1−x are

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RESULTS AND DISCUSSION Preparation and Characterization of Defective Metal Oxide Semiconductors. To prepare defective MoO3, TiO2, and ZnO, ascorbic acid was chosen as the reductant. As shown in Figure 2a, the pristine MoO3 has a pale cyan color. However, after grinding with ascorbic acid for 1 h, the resulting MoO3 samples exhibit a blue color, suggesting that a chemical transformation occurs. The XRD peaks for ascorbic acidtreated MoO3 samples can be indexed to the orthorhombic H0.5MoO3 (JCPDS No. 14−0041), indicating that hydrogen atoms are successfully doped into the crystal of H0.5MoO3 B

DOI: 10.1021/acssuschemeng.9b00374 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

shows a blue color and strong optical absorption from visible to near-infrared region with an absorption peak at 775 nm (Figure 3f). The absorption peak of H0.5MoO3 dispersion is owing to LSPR.24,36 Kinetic Analysis for Mechanochemical Synthesis of H0.5MoO3. The exceptional LSPR absorption of H0.5MoO3 allows us to analyze the mechanochemical process. Figure 4a

Figure 3. Structural characterization for the H0.5MoO3. (a, b) SEM images, (c,d) high-resolution Mo 3d XPS spectra, (e) FT-IR spectra, and (f) UV−vis absorption spectra of MoO3 and H0.5MoO3 dispersion.

Figure 4. Time-resolved monitoring of the production of H0.5MoO3. (a) Successive UV−vis absorption spectra of mechanochemical synthesis of H0.5MoO3. (b) The fitting of conversion fraction (α) as the function of reaction time for B1 solid-state reaction model.

studied by SEM as shown in Figure S3−S10. The results confirm the successful preparation of TiO2‑x and ZnO1−x. Intuitively, the surface of H0.5MoO3 from the ascorbic acidtreated MoO3 may contain ascorbic acid molecules because Mo atoms can coordinate with hydroxyl groups of ascorbic acid. To validate it, we use FTIR spectroscopy to characterize the surface composition of H0.5MoO3. The FTIR spectrum of MoO3 displays two peaks at 995 and 870 cm−1 (Figure 3e), corresponding to stretching vibrations of the terminal Mo = O and Mo−O−Mo bridging bonds.35 There is no absorption peak of MoO3 in the wavenumber range of 3000−1000 cm−1. In contrast, the FTIR spectrum of H0.5MoO3 shows additional absorption peaks at 3423, 2929, 1679, and 1095 cm−1, which are attributed to the stretching vibrations of O−H, C−H, C C, and C−O bonds of ascorbic acid, respectively. The results affirm the presence of ascorbic acid on the surface of H0.5MoO3, which enables its water-solubility. Likewise, the resulting TiO2‑x and ZnO1−x are also water-soluble as show in Figures S11 and S12. Apart from ascorbic acid, other mild reducing agents such as glutathione (GSH), cysteine (Cys), Dglucose (Glu), and α-lactose (Lac) are used for preparation of H0.5MoO3. Nevertheless, the UV−vis absorption of MoO3 treated with these substances are much lower than that of ascorbic acid-treated MoO3 (Figure S13). This suggests that the ascorbic acid is an ideal agent for synthesis of H0.5MoO3. It should be noted that AA is able to reduce the MoO3 dispersion to form oxygen-vacancy-rich MoO3 (MoO3‑x) nanosheet in the solution state with the assistance of the strong acid (pH 2).33,34 However, here AA directly reacts with MoO3 to generate H0.5MoO5 rather than MoO3‑x, suggesting that the reaction of AA and MoO3 undergoes different pathways in the solution and solid states, respectively. The present H0.5MoO3 dispersion

depicts the successive UV−vis absorption spectra for the generation of plasmonic H0.5MoO3. We fit the time dependence of the conversion fraction (α) to ten solid-state reaction mathematical models, including Prout-Tompkins B1, AvramiErofe’ev models (A2, A3, and A4), geometrical contraction models (R2 and R3), and diffusion models (D1, D2, D3, and D4) as shown in Figures 4b and S14.24,37 It can be seen that the best fit is obtained using B1 model (Figure 4b), testifying that this reaction for mechanochemical synthesis of H0.5MoO3 kinetically follows an autocatalysis model. The reason may be that the resulting water promotes the ascorbic acid dissociation to create hydrogen ions, which is beneficial to the hydrogen-doping reaction pathway. As well, we fit the conversion fraction data to a general Johnson-MehlAvrami−Kolmogorov (JMAEK) equation to determine the rate constant (k) as k = 1.4 × 10−3 min−1 (Figure S15).38 Visual Colorimetric Detection of H2O2 Based on Plasmonic H0.5MoO3. Based on the LSPR absorption ofH0.5MoO3 dispersion, the H0.5MoO3 provides a platform for visual colorimetric detection of oxidants. The introduction of oxidants is capable of oxidizing Mo5+ to form Mo6+, which decreases the surface free carrier concentration and therefore diminishes LSRP absorption.39,40 As a demonstration, H2O2 is selected as the model analyte because it possess an important biological function. Exposure of H0.5MoO3 dispersion to H2O2 results in the absorbance decrease at 775 nm (Figure 5a) because the oxidation process degenerates hydrogen and reduces the free carrier concentration on the surface of H0.5MoO3. As presented in Figure 5b, the absorbance of H0.5MoO3 dispersion at 775 nm gradually decreases upon increasing H2O2 concentration. Moreover, a strong linear C

DOI: 10.1021/acssuschemeng.9b00374 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Research Article

ACS Sustainable Chemistry & Engineering

process follows B1 solid reaction model. Furthermore, the resulting H0.5MoO3 dispersion is successfully employed for visual colorimetric detection of H2O2 as well. The present new mechanochemical synthesis approach for metal oxide semiconductors has significant advantages, such as universality, simpleness, high efficiency, and scalability. The obtained defective MoO3, TiO2, and ZnO will find more efficient and important applications in photocatalysis, biosensing, drug delivery, energy storage and conversion, and so forth.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.9b00374.

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Figure 5. Detection performance of H0.5MoO3 dispersion. (a) UV− vis absorption spectra of H0.5MoO3 dispersion in the absence and presence of H2O2. (b) UV−vis absorption spectra of H0.5MoO3 dispersion in the presence of different concentrations of H2O2. (c) The logarithm of absorbance change (A0−A) as a function of H2O2 concentrations in the range of 0.05−3 mM, where A0 and A are the absorbance values of H0.5MoO3 dispersion at 775 nm in the absence and presence of H2O2, respectively. (d) Colorimetric responses of H0.5MoO3 dispersion toward H2O2 and various potential interferents.

Optical and SEM images, UV−vis absorption spectra, FTIR spectra, and XPS spectra (Figures S1−S18) (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Yi He: 0000-0002-9324-3305 Liang Bian: 0000-0002-2769-7018 Author Contributions

R.L. carried out the experiments. R.L. and J.W. drew these illustrations. B.L. interpreted the data. F.D. and L.B. provided reagents/materials/analysis tools. Y.H. interpreted the data and wrote the manuscript. All authors reviewed the manuscript.

relationship is obtained between the logarithm of absorbance change and H2O2 concentration spanning from 0.05 to 3 mM (Figure 5c). The limit of detection (LOD) is about 30 μM at the signal-to-noise ratio of 3, which is comparable to that of the reported colorimetric assay.41,42 Interestingly, an apparent color change from blue to colorless is observed when the detection system contains 3 mM H2O2, which can be utilized for visual detection of H2O2 by the naked eye. Notably, the present colorimetric assay manifests an appreciable selectivity toward H2O2. The introduction of a series of potential interferents, including small organic molecules (dithiothreitol (DTT), glucose (Glu), threonine (Thr), and sucrose (Suc)), reductive polymer (polyethylene glycol (PEG)), as well as conventional inorganic ions (Mg2+, Mn2+, Zn2+, Na+, K+, NH4+, Cl−, Br−, NO3−, SO42−, SO32−, and SO32−), leads to a negligible colorimetric response (Figure 5d). Certainly, when the oxidants that have stronger oxidation property than that of H2O2 such as NaClO and KMnO4, they will result in apparent absorbance change at 775 nm (Figure S16). However, these oxidants cannot coexist with H2O2 because they are easy to react with H2O2 by redox reaction. What is more, the resulting ZnO1−x and TiO2‑x can also respond to oxidants such as H2O2, KMnO4, and Fe3+ as shown in Figures S17 and S18.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The support of this research by the National Natural Science Foundation of China (21705134, 41872039, and 41831285), One-Thousand-Talents Scheme in Sichuan Province, Sichuan Science and Technology Program (2018JY0462), and Longshan academic talent research supporting program of SWUST (Grant No. 18LZX204 and 17LZX449) is gratefully acknowledged.

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CONCLUSIONS In conclusion, we have developed a mechanochemical synthesis avenue for environmentally friendly preparation of defective MoO3, TiO2, and ZnO at room temperature. Our investigations reveal that the H0.5MoO3 and vacancy-rich TiO2 and ZnO in 10 g quantities can be easily obtained by grinding with ascorbic acid. The H0.5MoO3 dispersion displays unique LSPR absorption with a blue color. Simultaneously, the enhanced visible-light absorption from defective TiO2 and ZnO is found. The kinetic analysis suggests that the production D

DOI: 10.1021/acssuschemeng.9b00374 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acssuschemeng.9b00374 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX