Interface Functionalized MoxTi1–xO2−δ Composite via a Postgrowth

Jun 6, 2019 - Direct methanol fuel cells (DMFCs) are considered as the most promising solution ..... Certain reagents and physical and electrochemical...
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Article Cite This: ACS Appl. Energy Mater. 2019, 2, 4882−4889

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Interface Functionalized MoxTi1−xO2−δ Composite via a Postgrowth Modification Approach as High Performance PtRu Catalyst Support for Methanol Electrooxidation Jia-Long Li,† Lei Zhao,† Su-E. Hao,*,† and Zhen-Bo Wang*,† †

MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, No. 92 West-Da Zhi Street, Harbin 150001, China

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S Supporting Information *

ABSTRACT: Molybdenum modified interface functionalized MoxTi1−xO2−δ nanoparticles (IF-MTNPs) were obtained successfully through a postgrowth process of pristine TiO2 (p-TNPs) under the mild alkaline hydrothermal treatment without any annealing process based on etching and regrowth at the interface of p-TNPs. The hierarchical structure was fabricated with a crystalline core and an amorphous Mo doped interface. PtRu supported on an IF-MTNPs-C composite (incorporate with carbon black) catalyst was synthesized employing a polyol reduction process. The resultant PtRu/IF-MTNPs-C catalyst exhibits 3.4 times higher mass activity (0.71 A mg−1 Pt) toward methanol electrooxidation and improved durability (9.3 %) than that of the unmodified PtRu/p-TNPs-C catalyst owing to uniform dispersion and ultrafine-sized PtRu NPs. These favorable features are ascribed to unique merits of IF-MTNPs composite benefiting from modification of Mo at the support interface including the improved electron conductivity and enhanced electron interactions with PtRu NPs based on a strong metal support interaction (SMSI) mechanism. This work suggests the great capacity of an interfacial functionalized support material in application of direct methanol fuel cells. KEYWORDS: Interface functionalization, TiO2, Mo doping, PtRu electrocatalyst, Methanol electrooxidation

1. INTRODUCTION Direct methanol fuel cells (DMFCs) are considered as the most promising solution of increasingly energy shortage and environmental pollution for their merits of high energy densities, low operating temperatures, and ease of fuel transportation and storage.1−6 In recent decades, considerable efforts have been made and conspicuous achievement in both theoretical approaches and practical attempts has been achieved.3,7−9 However, obstacles to large-scale commercialization of DMFCs are still not solved, and practical improvements with the manufacturing cost and extended operation durability are imperative.10−13 The bimetallic catalyst of platinum and ruthenium (PtRu) is regarded as the most suitable anode material in DMFCs.14−17 Despite the bifunctional mechanism benefits, sluggish kinetics of the methanol electrooxidation reaction (MOR) and the tolerance against COads poisoning,16,18−23 the rarity and high cost of PtRu precious metal greatly hampers production and extensive © 2019 American Chemical Society

applications. An essential aspect of minimizing the dosage of PtRu is dispersing the nanoparticles (NPs) on appropriate supports5,13,24−27 with large surface area to attain maximum utilization. At present, carbon black is the most extensively applied support due to its high surface area, remarkable electrical conductivity, and low cost.13,28−30 Whereas the natural attributes of carbon lead to the structural corrosion during continuous operation in the environment, insufficient interactions between PtRu NPs and support result in performance degradation of the catalyst itself.13,28,29 Great efforts have been made to investigate an alternative support with comparable conductivity as well as improved resistance to corrosion. Transition metal oxides (MOs) are considered to be an Received: March 19, 2019 Accepted: June 6, 2019 Published: June 6, 2019 4882

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

Article

ACS Applied Energy Materials

2.3. Physical Characterization and Electrochemical Measurement. The morphologies of the samples were observed by a field emission transmission electron microscope (TEM) with high resolution TEM (HRTEM, FEI Tecnai G2 F20). Energy dispersive X-ray spectrometry (EDAX) was obtained with a Hitachi S4800 scanning electron microscope. X-ray diffraction (XRD) detection was operated on the D/max-RB diffractometer. X-ray photoelectron spectroscopy (XPS) analysis was conducted by a physical electronics PHI model 5700 instrument. Electrochemical evaluations were executed on a CHI 650E electrochemical analysis instrument by a standard three-electrode cell at 25 °C, using a glassy carbon disk electrode loaded with target catalyst, Hg/Hg2SO4 (0.68 V relative to reversible hydrogen electrode, RHE), and a platinum mesh, as working, reference, and counter electrodes, respectively. Within this paper, all potentials are presented with respect to RHE. More detailed information with material fabrication, electrode preparation, physical analysis, and electrochemical measurement is provided in the Supporting Information.

alternative support for their stability, strong interaction with PtRu NPs, and economy.27,31−38 While these merits of MOs support are apparent, inherent insufficiency in electric conductivity greatly impede the practical applications.33,36,38−43 In our previous work,17,41−46 we developed strategies in both composition and construction which exhibit superior performance in activity and durability. As doping with appropriate dopants has been investigated as an effective approach to modulate the band structure of MOs and enhance the electron transport,27,47 this modification route for MOs supports is expected to be further demonstrated. Herein, we reported a postgrowth doping route to the pristine TiO2 nanoparticles (p-TNPs) under the hydrothermal environment. The modification process under a mild reductive basic solution consisted of etching and regrowth at the interface, and the dopants are incorporated into the newly grown amorphous shell simultaneously. The Mo-doped MoxTi1−xO2−δ nanoparticles (IF-MTNPs) were successfully obtained with a crystalline core and interfacial functionalized shell. The PtRu NPs were deposited on the composite of IFMTNPs and carbon black via a polyol reduction process. Uniform dispersion and fine-sized PtRu NPs on the prepared PtRu/IF-MTNPs-C catalyst were determined and exhibit 3.3 times higher mass activity for MOR and 10.3% improved durability over undoped PtRu/p-TNPs catalyst. The structure and properties of IF-MTNPs have been characterized in detail, and the effect on the enhanced performance of PtRu/IFMTNPs-C catalyst for MOR has also been investigated. These findings indicate the potential application of interfacial functionalized MOs support and its crucial effects in promoting the performance of DMFCs anode catalyst, which is of great significance in commercialization.

3. RESULTS AND DISCUSSION Scheme 1 illustrated the modification steps of IF-MTNPs support, which including two principal aspects: first, etching at Scheme 1. Schematic Illustration of the IF-MTNPs Postgrowth Modification Process

2. EXPERIMENTAL SECTION 2.1. Fabrication of Interface Functionalized MoxTi1−xO2−δ Nanoparticles (IF-MTNPs). The interfacial functionalized method was employed under a mild reductive alkaline hydrothermal treatment.48 Typically, 200 mg of the pristine TiO2 NPs was dispersed in 150 mL of deionized (DI) water which dissolved with 0.435 g of hydroxylamine hydrochloride (NH2OH·HCl) and 0.72 g of sodium sulfide nonahydrate (Na2S·9H2O) followed by adding 0.531 g ammonium molybdate tetrahydrate ((NH4)6Mo7O24·4H2O). Then, the mixture was moved into a Teflon-lined stainless steel autoclave which was treated at 180 °C for 10 h in the continuously rotating condition. After cooling down naturally, the mixture was filtered and decontaminated with DI water several times, and dried under vacuum at 80 °C, which noted as IF-MTNPs. For a benchmark, the undoped sample was obtained with the reaction solution of only NH2OH·HCl and Na2S, which was noted as IF-TNPs. 2.2. Synthesis of PtRu/IF-MTNPs-C Catalyst. The PtRu NPs depositing on IF-MTNPs-C composite were synthesized via a microwave-assisted polyol process (MAPP).17,41,42 Briefly, 15 mg prepared IF-MTNPs and 15 mg XC-72 carbon black were dispersed into the 60 mL solution which was mixed with ethylene glycol (EG) and isopropyl alcohol (4:1) with ultrasonication for 1 h. Then, the designed amounts of H2PtCl6/EG and RuCl3/EG solution was respectively added in drops with agitation for over 3 h. The pH value of the mixture was adjusted to 8.0 by adopting 1 mol L−1 NaOH/EG solution. After heating by microwave for 50 s under Ar atmosphere, the suspension was placed at room temperature and the pH was adjusted to 2 by HNO3 aqueous solution with subsequent stirring for 12 h. The final catalyst was obtained by decontaminating several times with ultrapure water (Millipore, 18.2 MΩ·cm) and then vacuum-dried at 60 °C. The mass content of PtRu in the as-prepared catalyst is 20% with the atomic ratio of Pt/Ru 1:1.

the interface of p-TNPs under the weakly alkaline and reductive hydrothermal environment. Then, regrowth of TiO2 at the interface was executed subsequently and Mo dopants were incorporated into the newborn amorphous shells simultaneously. This unique postgrowth doping route generates an interfacial functionalized TiO2 support with a crystalline core and a Mo doped amorphous interface. The crystal structure of modified support was detected by XRD analysis. The diffraction patterns of IF-MTNPs, IF-TNPs (modified without Mo), and p-TNPs in Figure 1a indicate the good indexation into an anatase TiO2 phase (JCPDS No. 89− 4921). In comparison with pristine TNPs, no additional peaks related to molybdenum oxides or sulfides are observed in IFMTNPs or IF-TNPs. Slight shift in the (101) peak of IFMTNPs is found in Figure 1b, which suggested a small relaxation in the crystal lattice. The cell parameters calculated from XRD patterns were determined in Table 1. The lattice constants of p-TNPs and IF-TNPs are nearly the same, which inferred that the etching and regrowth behavior do not affect the cell structure. However, the Mo doping leads to an expanded effect in the c parameter especially. It implies the substitution of Mo dopant into the crystal lattice of TiO2 and the modulation in band structure which facilitates the charge transfer.47,49,50 The morphology of as-prepared PtRu catalyst was illustrated by a transmission electron microscope (TEM). Figure 2a shows the high resolution TEM (HRTEM) image of PtRu/IF4883

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

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ACS Applied Energy Materials

Figure 1. XRD patterns of pristine TNPs and modified supports (a); local amplification of TiO2 (101) range (b).

dopant of Mo is demonstrated by EDAX analysis. The characteristic peak of Mo can be identified in Figure S2, and the determined element contents are listed in Tables S1 to S3. The PtRu content of the catalyst corresponds to the theoretical values of 20 wt % with atomic Pt/Ru of 1:1. The surface elemental composition of PtRu/IF-MTNPs-C was interrogated by X-ray photoelectron spectroscopy (XPS) and elemental analysis was conducted. As depicted in Figure 3a, elements of Pt, Ru, Ti, Mo, O, and C can be assigned in the wide-scan spectrum. Especially, the Mo 3d characteristic peak is illustrated in Figure 3e. The determined surface component of each catalyst is provided in Table S4, which is further proof of the existence of the discussed elements, especially the Mo at surface, and is consistent with the analysis of XRD and EDAX above. Additionally, the fitting results with Pt 4f core level spectrum of PtRu/C, PtRu/p-TNPs-C, and PtRu/IF-MTNPsC are illustrated in Figure 3b−d. The peak position and components calculated from the curve fitting are summarized in Table 2. A shift of Pt 4f binding energy to the lower values by 0.2 and 0.1 eV of PtRu/IF-MTNPs-C catalyst can be noticed, comparing with that of the PtRu/C and unfunctionalized PtRu/p-TNPs-C respectively. This kind of binding energy shift implies the modulation in electron structure of PtRu NPs, which is considered to be the root of strong metal support interaction (SMSI).33,41,42,52 It is observed that the electronic interaction of IF-MTNPs-C support with PtRu NPs is stronger than that of p-TNPs-C support. To further analyze this electron donation behavior, the core level spectrum of Mo is shown in Figure 3f, which exhibits a mixed valence state of Mo (VI) and Mo (V) with 3d5/2 and 3d3/2 double peaks, respectively. The deconvolution of Mo 3d spectra and the determined peak position and component with that of analogous catalysts reported in the literature53,54 are summarized in Table S5. As listed in Table S5, a mixed valence state of Mo (V) and Mo (VI) at the interface is determined to be 67.2% and 32.8%, respectively, which reveals a balanced state and this variable valence state endowing the electron donation capacity. For comparative analysis, the valence state of Mo (VI) and Mo (V) with a MoOx supported catalyst and MoOx/C is cited and illustrates that the chemical state of Mo in PtRu/IF-MTNPs-C is different from Pt/MoOxRGO catalyst and MoOx/C composite.53,54 A negative shift of over 0.6 eV in Mo (VI) binding energy is observed compared to the Mo (VI) in Pt/oxides-RGO catalyst and a positive shift of 0.3 eV comparing to Mo (V) oxides/C, which further proves

Table 1. Cell Parameters Calculated from XRD Patterns Determined Lattice Constants Sample

a (Å)

c (Å)

Cell Volume (Å3)

p-TNPs IF-TNPs IF-MTNPs

3.7832(0) 3.7831(3) 3.7852(0)

9.5116(6) 9.5104(9) 9.5246(4)

136.14 136.11 136.47

Figure 2. HRTEM images of the PtRu/IF-MTNPs-C (a) and PtRu/ p-TNPs-C (b) catalysts. TEM images of PtRu/IF-MTNPs-C (c), PtRu/p-TNPs-C (d), and PtRu/C (e).

MTNPs-C, in which two clear lattice spacings of 0.350 and 0.235 nm corresponding to (101) and (001) of anatase TiO2 can be identified, respectively.50 As for the HRTEM image of PtRu/p-TNPs-C in Figure 2b, only the lattice fringes of anatase TiO2 (101) plane can be detected. Moreover, lattice spacing of 0.221 nm corresponding to Pt (111) plane8,51 can be seen in both Figure 2a and b, suggesting the successful deposition of PtRu NPs on the support. It is noticed that the PtRu NPs exhibit a distinct tendency to locate on the edge of oxide supports to form multiphase junctions, and the amorphous interface of IF-MTNPs can be clearly identified from Figure 2a. Intensive interactions between PtRu and IFMTNPs support can be concluded, and a more uniform deposition of PtRu NPs than that of PtRu/p-TNPs-C and as prepared PtRu/C can be depicted in Figure 2c,d,e. Further proof of the coexistence of PtRu, TiO2, and especially the 4884

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

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ACS Applied Energy Materials

Figure 3. XPS survey spectrum of as-prepared PtRu catalysts (a) and core level Pt 4f regions of PtRu/C (b), PtRu/p-TNPs-C (c), and PtRu/IFMTNPs-C (d). Mo 3d comparison (e) and core level Mo 3d region of PtRu/IF-MTNPs-C (f).

Table 2. Calculated Fitting Results of Pt 4f Core Level Spectrum of As-Prepared PtRu Catalyst Pt (0) Sample PtRu/IF-MTNPs-C PtRu/p-TNPs-C PtRu/C

Pt (II)

Pt (IV)

Orbital spin

Binding Energy (eV)

Relative Ratio (%)

Binding Energy (eV)

Relative Ratio (%)

Binding Energy (eV)

Relative Ratio (%)

4f 7/2 4f5/2 4f 7/2 4f5/2 4f 7/2 4f5/2

71.7 75.0 71.8 75.1 71.9 75.2

54.0

72.8 76.1 73.1 76.3 73.3 76.6

29.2

75.1 78.4 75.8 79.1 76.3 79.6

16.9

46.0 49.6

28.5 29.9

25.5 20.5

respectively, which shows an intensive enhancement in catalytic activity of PtRu/IF-MTNPs-C catalyst comparing to 3.4 times higher than that of PtRu/p-TNPs-C catalyst and 1.15 times higher than that of PtRu/C shown in Figure S2a. It is worth mentioning that PtRu/IF-MTNPs-C catalyst shows comparable catalytic activity toward methanol electrooxidation in acid medium compared to those reported in recent literature,17,36,56,57 which is summarized in Table S6. Meanwhile, the PtRu/IF-MTNPs-C catalyst has a lower onset potential of less than 0.29 V compared to that of 0.35 V of asprepared PtRu/C catalyst and is close to the onset potential of 0.35 V with commercial PtRu/C (E-tek) and PtRu/C-TiO2 catalyst.36 This indicates that the mass activity of PtRu/pTNPs-C is lower than that of Mo interfacial functionalized catalyst resulting from insufficient interaction with PtRu NPs and its inherent lack of charge transport. Nevertheless, postgrowth doping of Mo at the interface of TiO2 reconciles this obstacle through an electric transfer mechanism demonstrated above. The COad stripping voltammograms of the PtRu/IFMTNPs-C and PtRu/p-TNPs-C catalyst are depicted in Figure 4b. The electrochemically active surface area (ECSA) is

that the Mo infiltrates into the interface of TiO2. As XRD analysis reveals that no molybdenum oxides or sulfides are detected, it indicates the incorporation of Mo5+/Mo6+ into the lattice of Ti site of TiO 2. Therefore, the interfacial functionalization of Mo into the TiO2 promotes the electron transport27,47 from support to PtRu NPs and enhances the anchoring effects which lead to the distinct tendency to form multiphase junctions detected by the HRTEM analysis above. Simultaneously, the electric transfer mechanism results in the higher content of Pt (0) in PtRu/IF-MTNPs-C catalyst than that of unmodified ones, which increased 8.0% and 4.4% compared to PtRu/p-TNPs-C and PtRu/C, respectively. With the superior corrosion resistance of Pt (0) over that of Pt(II) and Pt(IV),55 it is believed that PtRu/IF-MTNPs-C catalyst possesses high performance in electrocatalysis. The methanol electrooxidation reaction (MOR) is the essential process within DMFCs. Figure 4a illustrates the cyclic voltammograms (CV) cures of PtRu/IF-MTNPs-C and PtRu/ p-TNPs-C catalyst in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 at 25 °C with scanning rate of 0.05 V·s−1. The forward peak current densities of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst are 0.71 and 0.21 A·mg−1 Pt, 4885

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

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ACS Applied Energy Materials

Figure 4. Cyclic voltammogram cures of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 at 25 °C with scanning rate of 0.05 V·s−1 (a). COad stripping voltammograms of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst in a solution of 0.5 mol L−1 H2SO4 at 25 °C with scanning rate of 0.05 V·s−1 (b). Nyquist plots of EIS for PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 (c). Chronoamperometric curves for PtRu/IF-MTNPs-C and PtRu/p-TNPsC catalyst in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 at a fixed potential of 0.6 V vs RHE (d).

with interfacial functionalized support in the form of charge transfer of support and enhanced interactions with PtRu NPs, which synergistically generates a shift in the d-band center and bifunctional mechanism. Durability of the PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst is evaluated preliminary via the chronoamperometric measurement at a constant potential of 0.65 V for 3600 s shown in Figure 4d. The current densities of PtRu/IF-MTNPsC catalyst is higher than that of PtRu/p-TNPs-C catalyst throughout the entire operation time. MOR current density of PtRu/IF-MTNPs-C catalyst after 3600 s remains 0.02 A·mg−1 Pt, which is over 6 times higher than that of PtRu/p-TNPs-C catalyst. Further evaluation of stability is performed by accelerated potential cycling test (APCT); the CV of composite supported catalyst is presented in Figure 5 and Figure S2. After the first 200 cycles of scanning, all as-prepared catalyst illustrated a sharp decline, and PtRu/IF-MTNPs-C catalyst lost 50.7% of initial activity, which is better than the 60.0% loss of PtRu/p-TNPs-C and 59.5% loss of PtRu/C throughout the APCT. The size evaluation of PtRu NPs before and after APCT is reflected by TEM investigation. The morphology evolution and size distribution of PtRu/IFMTNPs-C and PtRu/p-TNPs-C catalyst throughout APCT is shown in Figure 6. Identical growth in particle size is detected in both the discussed catalysts after 1000 cycles of voltammograms, which is considered be the reason for performance degradation. The size distribution analyzed from TEM images suggested the PtRu NPs on IF-MTNPs-C grow to 3.13 nm after APCT, which shows 26.2% growth from

determined by the recognized approach based on the COstripping voltammetry curve.58 The ECSA of PtRu/IFMTNPs-C and PtRu/p-TNPs-C catalyst is about 50.8 and 50.2 m2 g−1. Regarding the mass activity, the specific activities of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst are calculated to be 13.9 and 4.2 A·m−2 which is 3.7 times higher. Compared to the 3.3 times higher mass activity, the nearly identical magnitude higher specific activity implies that the enhanced activity of PtRu/IF-MTNPs-C is mostly attributed to electric transfer behavior from the Mo interface functionalized support to the PtRu NPs and facilitates an enhanced SMSI.33,52 In addition, the peak potential of oxidation of COads on PtRu/IF-MTNPs-C catalyst exhibits a negative shift of 136 mV compared to that of PtRu/p-TNPs-C catalyst. The onset potential of COads oxidation of PtRu/IF-MTNPs-C catalyst is 83 mV lower than that of PtRu/C, which is shown in Figure S2b. This indicates the higher ability to electro-oxidize the COads originating from electronic transfer and enhanced SMSI. The kinetic properties of MOR are assessed with the electrochemical impedance spectroscopy (EIS). The Nyquist plots of methanol electrooxidation on PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst electrodes in acidic methanol solution are shown in Figure 4c. As the main arc appears in the medium frequency range relating to the electro-oxidation of methanol, it is obvious that the charge transfer resistance of PtRu/IF-MTNPs-C is much lower than that of PtRu/p-TNPsC catalyst, suggesting a much faster charge transfer capacity toward MOR. The superior MOR kinetic performance of PtRu/IF-MTNPs-C is also attributed to the electron behavior 4886

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

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ACS Applied Energy Materials

Figure 5. CV of PtRu/IF-MTNPs-C (a) and PtRu/p-TNPs-C (b) catalyst in a solution of 0.5 mol L−1 CH3OH and 0.5 mol L−1 H2SO4 before and after APCT at 25 °C with canning rate of 0.05 V·s−1. Mass activities of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst with cycle numbers during APCT (c). Normalization of initial forward peak current density of PtRu/IF-MTNPs-C and PtRu/p-TNPs-C catalyst with cycle numbers during APCT (d).

Figure 6. TEM images with associated PtRu NPs size distribution of PtRu/IF-MTNPs-C (c, d, f) and PtRu/p-TNPs-C (a, b, e) catalyst before and after APCT.

4. CONCLUSIONS

its initial size, whereas 2.5 times growth of PtRu NPs on pTNPs-C is investigated. Additionally, the final size of PtRu/IFMTNPs-C is much smaller than that of PtRu/p-TNPs-C. Fine size and absence of agglomeration in PtRu NPs can be determined with the interface functionalized catalyst, while the severe agglomeration of PtRu NPs is found in PtRu/p-TNPs-C catalyst after APCT, which results from the lack of enhanced electron interactions.

In conclusion, interface functionalized MoxTi1−xO2−δ composite as high performance PtRu catalyst support for methanol electrooxidation was fabricated via a hydrothermal postgrowth doping strategy based on the etching and regrowth mechanism. Mild reductive basic solution facilitates the etching at the TiO2 interface, and the Mo dopants are incorporated into the regrown amorphous shell forming a unique structure of robust 4887

DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889

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ACS Applied Energy Materials

based power system architectures and control − A review. Renewable Sustainable Energy Rev. 2017, 73, 10−18. (8) Xu, J.; Guo, S.; Hou, F.; Li, J.; Zhao, L. Methanol oxidation on the PtPd(111) alloy surface: A density functional theory study. Int. J. Quantum Chem. 2018, 118 (3), e25491. (9) Xu, Q.; Zhang, F.; Xu, L.; Leung, P.; Yang, C.; Li, H. The applications and prospect of fuel cells in medical field: A review. Renewable Sustainable Energy Rev. 2017, 67, 574−580. (10) Chung, D. Y.; Yoo, J. M.; Sung, Y. E. Highly Durable and Active Pt-Based Nanoscale Design for Fuel-Cell Oxygen-Reduction Electrocatalysts. Adv. Mater. 2018, 30, 1704123. (11) Lu, Y.; Du, S.; Steinberger-Wilckens, R. One-dimensional nanostructured electrocatalysts for polymer electrolyte membrane fuel cellsA review. Appl. Catal., B 2016, 199, 292−314. (12) Wu, J.; Xiao, Z. Y.; Martin, J. J.; Wang, H.; Zhang, J.; Shen, J.; Wu, S.; Merida, W. A review of PEM fuel cell durability: Degradation mechanisms and mitigation strategies. J. Power Sources 2008, 184 (1), 104−119. (13) You, P. Y.; Kamarudin, S. K. Recent progress of carbonaceous materials in fuel cell applications: An overview. Chem. Eng. J. 2017, 309, 489−502. (14) Bock, C.; Paquet, C.; Couillard, M.; Botton, G. A.; Macdougall, B. R. Size-selected synthesis of PtRu nano-catalysts: reaction and size control mechanism. J. Am. Chem. Soc. 2004, 126 (25), 8028. (15) Liu, Z.; Ling, X. Y.; Su, X.; Lee, J. Y. Carbon-Supported Pt and PtRu Nanoparticles as Catalysts for a Direct Methanol Fuel Cell. J. Phys. Chem. B 2004, 108 (24), 8234−8240. (16) Rolison, D. R.; Hagans, P. L.; Swider, K. E.; Long, J. W. Role of Hydrous Ruthenium Oxide in Pt−Ru Direct Methanol Fuel Cell Anode Electrocatalysts: The Importance of Mixed Electron/Proton Conductivity. Langmuir 1999, 15 (3), 774−779. (17) Sui, X.-L.; Li, C.-Z.; Zhao, L.; Wang, Z.-B.; Gu, D.-M.; Huang, G.-S. Mesoporous g-C3N4 derived nano-titanium nitride modified carbon black as ultra-fine PtRu catalyst support for Methanol electrooxidation. Int. J. Hydrogen Energy 2018, 43 (10), 5153−5162. (18) Gasteiger, H. A.; Marković, N.; Ross, P. N.; Cairns, E. J. Electro-oxidation of small organic molecules on well-characterized PtRu alloys. Electrochim. Acta 1994, 39 (11), 1825−1832. (19) Huang, L.; Zhang, X.; Wang, Q.; Han, Y.; Fang, Y.; Dong, S. Shape-Control of Pt−Ru Nanocrystals: Tuning Surface Structure for Enhanced Electrocatalytic Methanol Oxidation. J. Am. Chem. Soc. 2018, 140 (3), 1142. (20) Ling, Y.; Yang, Z.; Yang, J.; Zhang, Y.; Zhang, Q.; Yu, X.; Cai, W. PtRu nanoparticles embedded in nitrogen doped carbon with highly stable CO tolerance and durability. Nanotechnology 2018, 29 (5), 055402. (21) Wang, Q.; Wang, G.; Tao, H.; Li, Z.; Han, L. Highly CO tolerant PtRu/PtNi/C catalyst for polymer electrolyte membrane fuel cell. RSC Adv. 2017, 7 (14), 8453−8459. (22) Yang, P.; Yuan, X.; Hu, H.; Liu, Y.; Zheng, H.; Yang, D.; Chen, L.; Cao, M.; Xu, Y.; Min, Y. Solvothermal Synthesis of Alloyed PtNi Colloidal Nanocrystal Clusters (CNCs) with Enhanced Catalytic Activity for Methanol Oxidation. Adv. Funct. Mater. 2018, 28 (1), 1704774. (23) Huang, W.; Kang, X.; Xu, C.; Zhou, J.; Deng, J.; Li, Y.; Cheng, S. 2D PdAg Alloy Nanodendrites for Enhanced Ethanol Electroxidation. Adv. Mater. 2018, 30 (11), 1706962. (24) Sharma, S.; Pollet, B. G. Support materials for PEMFC and DMFC electrocatalystsA review. J. Power Sources 2012, 208 (2), 96−119. (25) Esfahani, R. A. M.; Ebralidze, I. I.; Specchia, S.; Easton, E. B. A fuel cell catalyst support based on doped titanium suboxides with enhanced conductivity, durability and fuel cell performance. J. Mater. Chem. A 2018, 6 (30), 14805. (26) Zhao, L.; Sui, X. L.; Li, J. Z.; Zhang, J. J.; Zhang, L. M.; Huang, G. S.; Wang, Z. B. Supramolecular Assembly Promoted Synthesis of Three-Dimensional Nitrogen Doped Graphene Frameworks as Efficient Electrocatalyst for Oxygen Reduction Reaction and Methanol Electrooxidation. Appl. Catal., B 2018, 231, 224.

core and functional Mo doped interface. Based on the electron transport mechanism with SMSI, the Mo functionalization occured at the interface enhancing the electronic donation from modified support to PtRu NPs. As the electron donor, Mo functionalization facilitates electron donation to the PtRu NPs, as well as modulating the band structure of pristine TiO2 support resulting in the promotion of electronic conductivity. Depending on the superior properties of IF-MTNPs composite support, high performance PtRu/IF-MTNPs-C catalysts are obtained with excellent activity and durability toward MOR. We believe that interfacial functionalized MOs support is of great importance to the commercialization of DMFCs.



ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.9b00591.



Certain reagents and physical and electrochemical characterizations (PDF)

AUTHOR INFORMATION

Corresponding Authors

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

Zhen-Bo Wang: 0000-0001-9388-1481 Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS We acknowledge the National Natural Science Foundation of China (Grant No. 21273058, 21673064, 51802059, and 21503059), China postdoctoral science foundation (Grant No. 2018M631938, 2018T110307, and 2017M621284), Heilongjiang Postdoctoral Fund (LBH-Z17074 and LBHZ18066) and Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2019040 and 2019041).



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DOI: 10.1021/acsaem.9b00591 ACS Appl. Energy Mater. 2019, 2, 4882−4889