Visible-Light-Driven 3D Dendritic PtAu@Pt Core-Shell Photocatalyst

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Visible-Light-Driven 3D Dendritic PtAu@Pt Core-Shell Photocatalyst towards Liquid Fuel Electrooxidation Hui Xu, Pingping Song, Jin Wang, Yukihide Shiraishi, Yukou Du, and Qingyun Liu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b01228 • Publication Date (Web): 12 Apr 2018 Downloaded from http://pubs.acs.org on April 12, 2018

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ACS Sustainable Chemistry & Engineering

Visible-Light-Driven 3D Dendritic PtAu@Pt Core-Shell Photocatalyst towards Liquid Fuel Electrooxidation Hui Xu†, Pingping Song†, Jin Wang†, Yukihide Shiraishi‡, Yukou Du*†‡, and Qingyun Liu*∆ †

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P.R. China

‡

Tokyo University of Science Yamaguchi, Sanyo-Onoda-shi, Yamaguchi 756-0884, Japan ∆

College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, PR China * Corresponding author: Tel: 86-512-65880089, Fax: 86-512-65880089; E-mail: [email protected] (Y. Du). [email protected]

ABSTRACT Plasmonic photocatalysis, based on surface plasmon resonance (SPR) of bimetallic nanoparticles, has been exploited for various applications. We herein successfully synthesize an advanced class of three-dimensional (3D) dendritic core-shell PtAu@Pt photocatalysts, which can greatly promote the electrooxidation of liquid fuel. Interestingly, the optimized 3D core-shell PtAu@Pt photocatalysts exhibited outstanding elextrocatalytic activities towards MOR and EOR under the visible light irradiation, which are 1.9 and 1.8 times greater than that under the ambient reaction, respectively. The broad adsorption of plasmonic Au, electronic effects between Pt and 1 ACS Paragon Plus Environment

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Au, and high surface active areas of 3D dendritic structure greatly contribute to the improved photoelectrocatalytic performances. KEYWORDS: plasmonic photocatalysts; dendritic PtAu@Pt; visible light; liquid fuel oxidation; fuel cells INTRODUCTION Efficient utilization of solar energy is a sublime target and the pursuit of appropriate materials as photocatalysts with the highly efficient photocatalysis performances is also one of the forbidden challenges.1-2 Recent years, SPR effects in the metal nanostructures have attracted increasing attention for a variety of applications such as optical imaging, molecular sensing, and magnetism.3-4 In particular, the SPR effects for the application of photocatalysis currently has been one of the hottest topics which can efficiently converse the solar energy into the clean electrical energy in the form of hot electrons.

5-7

The motivation is largely driven by

the rapid depletion of energy and the growing demand of clean energy. Although some preliminary advances have been made in the study of photoelectrocatalytic oxidation reaction, the understanding of the visible light enhance electrocatalytic oxidation activity and stability, as well as the mechanism of electrochemical reaction, remains rather ambiguous.8-11 Understanding the mechanism in photo-assisted electrocatalytic oxidation still requires in-depth and broadening researches.12-14 However, up to now, there have been few reports on the enhancement of electrocatalytic activity, and stability based on visible light. More importantly, only a deep understanding of the mechanism of photo-assisted enhancement of 2 ACS Paragon Plus Environment

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electrocatalytic activity and stability is available, it is possible to provide feedback on practical

applications

scientific

guidance

for

obtaining

high-performance,

high-stability catalysts.15 Therefore, in order to use solar energy resources efficiently and mitigate the energy crisis, it is urgent to design a highly efficient photoelectrocatalyst and make a fully understanding of the photoelectrocatalytic mechanism. Impressively, some previously reported researches have revealed that the SPR mode of plasmonic metal nanoparticles greatly rely on the shape of plasmonic nanostructures.16-20 Accordingly, the architecture design of plasmonic nanostructures is a significant approach for improving the photocatalytic performances.21-22 In addition, the SPR of the metal nanoparticles is also greatly determined by the composition and size.23-25 Inspired by this, if we coupled Pt with Au to form the bimetal heterostructures with desirable shapes, it would greatly boost the promotion of photoelectrocatalytic performances towards liquid fuel.26-27 On the basis of the mentioned analyses, we herein demonstrated a facile approach for the preparation of 3D dendritic core-shell PtAu@Pt nanocrystals (NCs), which can serve as the highly efficient photocatalysts. Impressively, owing to highly exposed active areas, efficient electronic and synergistic effects, and efficient adsorption of visible light, the 3D dendritic PtAu@Pt nanocatalysts exhibited outstandingly high electrocatalytic activities towards MOR and EOR with the photoelectrocatalytic activities of 2291.4 mA mg-1 and 15.0 mA cm-2, 5760.3 mA mg-1 and 37.6 mA cm-2, 1.9 and 1.8 times greater than that under the ambient reaction, respectively. This work may offer guidance for constructing well-defined plasmonic metal nanostructures to 3 ACS Paragon Plus Environment


work as highly efficient photoelectrocatalysts for fuel cells with the assistance of visible light. EXPERIMENTAL SECTION Synthesis of 3D dendritic PtAu@Pt NCs In the standard preparation of 3D dendritic PtAu@Pt NCs, 50 mg sodium citrate (Na3CA) and 20 mg polyvinylpyrrolidone (PVP) were firstly added to a flask containing 10 mL deionized water. After ten minutes of continuous stirring, 1.40 mL H2PtCl6 (7.7 mM) and 0.45 mL HAuCl4 (24.3 mM) solutions were dropped to above homogeneous solution in sequence. The reaction was carried out by the sequential injection of 5 mL ascorbic acid (AA, 0.5 M) under gentle shaking. After continuous reaction for 5 min, the mixture was then sonicated for another half hour. Afterwards, the flask was heated to 60 °C with rapid stirring. The resultant products were centrifuged twice at 10000 rpm for 10 min, and the precipitate was re-dispersed into 10 mL deionized water for further use. For comparison, the Pt1Au1.5 and Pt1Au0.5 NCs were also produced following the same procedure, just with the amounts of involved HAuCl4 solution varied. Physicochemical characterizations The samples were characterized by the Tecnai G220 (FEI America) and FEI Tecnai F20 transmission electron microscopy (TEM). The X-ray diffraction (XRD) patterns of the samples were acquired using an X’Pert-Pro MPD diffractometer (Netherlands PANalytical) The X-ray photoelectron spectroscopy (XPS) were performed on a VG Scientific ESCALab 220XL electron spectrometer using 300 W 4 ACS Paragon Plus Environment

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Al Kα radiation. Electrochemical measurements The electrocatalytic activity of the MOR and EOR were performed at the scan rate of 50 mV s-1 from -0.9 to 0.3 V (vs SCE). The photocurrent responses of the 3D dendritic PtAu@Pt NCs were measured at the potential of -0.2 V (vs SCE). For evaluating their durability, the successive 500 cycles cyclic voltammetry (CV) of have also been conducted. All the working electrodes for photo-electrochemical tests were irradiated by a xenon lamp (150 W). RESULTS AND DISCUSSION The 3D dendritic PtAu@Pt NCs were produced by simultaneous reduction of HAuCl4 and partial H2PtCl6 precursors by using AA as reducing agent, PVP as both surfactant and structure-directing agent, respectively. The morphology of the resultant products was initially characterized by the TEM in the Figure 1. As seen, the TEM images (Figure 1a, b) showed that the as-obtained products consisted of uniform dendrite-like nanocrystals with a high yield. Importantly, the surface of each nanocrystal is of porous nanostructure with abundant granules. More interestingly, each nanocrystal surveyed is of two different regions that contrasted strongly with one another, indicating the possible presence of heterostructures in the nanocrystals. The remarkable features can also be clearly seen in the high-magnification TEM (HRTEM) image (Figure 1d). The HRTEM image shows the core interplannar spacing is 0.232 nm, which is consistent with the (111) plane of PtAu intermetallic structure,28 while the d-spacing of the dendritic shell is 0.228 nm, which is corresponding to the Pt (111) 5 ACS Paragon Plus Environment


plane, confirming the generation of the PtAu intermetallic core and dendritic Pt shell.29 To further identify this unique 3D dendritic PtAu@Pt structure, we have also employed a number of tools to characterize the nanostructures and analyze the element distribution. As seen in Figure 1c, the XRD patterns of the products exhibited two distinct sets of diffraction peaks, which are corresponding to typical face-centered cubic (fcc) crystalline of PtAu and Pt, suggesting the formation of heterostructure in the samples.30-31 Moreover, the diffraction peaks of PtAu alloy core located between standard Pt and Au, and the average crystalline sizes of PtAu core calculated by Scherrer equation was 11.4 nm, further confirming the presence of PtAu alloy core. Besides, the EDS element mapping (Figure 1e) on individual PtAu@Pt NCs indicated that Au and Pt atoms were well distributed over the whole nanocrystals. More significantly, the overlapping element mapping of Au and Pt also indicated that the intermetallic core mainly consisted of Au and Pt atoms, while the dendritic shell is composed of Pt atoms. It is evident that the Pt shell locates outside of the dendrite and distributes homogeneously on the surface, revealed by the line scans (Figure 1f). All of results have fully confirmed the successful fabrication of core-shell PtAu@Pt nanostructures.32 For understanding the difference in shape of PtAu NPs with different compositions, the morphologies of PtAu0.5 and PtAu1.5 NCs have also been recorded in Figure S1. As seen, similar with the 3D dendritic PtAu1 NCs, both PtAu0.5 NCs and PtAu1.5 NCs also showed the uniform dendrite-like shape, confirming t this approach was favorable for fabricating the unique 3D dendritic PtAu@Pt nanostructures with 6 ACS Paragon Plus Environment

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large scale.33-34

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Figure 1. (a, b) TEM images of 3D dendritic PtAu@Pt NCs. (c) XRD patterns of PtAu@Pt NCs, Pt and Au. (d) HRTEM image of an individual PtAu@Pt NCs. (e) The TEM EDS mapping, HAADF-STEM and corresponding (f) line-scan of PtAu@Pt NCs for element distribution analyses. For uncovering the formation mechanism of the 3D dendritic PtAu@Pt NCs, some controlled experiments have also been conducted. In the present reaction system, the selective addition of PVP played a key role in the controlled synthesis of such unique PtAu@Pt NCs.35 The reactions without PVP yielded some bulk materials, which are accumulating together (Figure S2). Furthermore, after a thoroughly investigation, we also found that the reaction without the heating treatment yielded some inhomogeneous nanostructures with less granular protuberances on the surface (Figure S3). For comparison, the TEM images of Pt/C catalysts have also been added. (Figure S4)


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Figure 2. The XPS spectra of (a) Pt 4f and (b) Au 4f in 3D dendritic PtAu1 NCs. (c) UV-vis spectra of 3D dendritic PtAu1 NCs, and (d) photocurrent responses of dendritic PtAu1 NCs towards MOR and EOR. To confirm the component of as-prepared products, the XPS characterizations of Pt 4f and Au 4f were also performed. From Figure 2a, we could see that the two peaks located at the binding energies (B.E.) around 71.7 and 74.5 eV were attributed to Pt 4f7/2 and 4f5/2 states, respectively, while the other two peaks presented at the B.E. around 72.1 and 75.3 eV are associated with Pt 4f7/2 and 4f5/2 peaks of Pt (II) species.36 Interestingly, The B.E. of Pt 4f7/2 displayed an apparently positive shift in comparison to the standard Pt (71.2 eV), indicating the charge transfer from Au to



Pt.37-38 Additionally, the two components of Au peak are visible at B.E. of 83.7 and 87.4 eV, which are corresponding to the Au 4f7/2 and Au 4f5/2, respectively.39 With regard to Au, the slight shift in the B.E. of Au 4f may be ascribed to the partial incorporation of Pt into Au, the analysis of XPS have also indicated the formation of core-shell PtAu@Pt nanostructures. The UV–vis adsorption test was conducted to study the optical properties of PtAu@Pt NCs, as shown in Figure 2c. The PtAu@Pt NCs displayed an absorption peak at around 515 nm, which was consistent with the adsorption peak of Au nanoparticles (~510 nm), suggesting that the PtAu@Pt nanocatalysts possessed promising superiorities to photoelectrocatalytic liquid fuel oxidation.40-42 Moreover, photocurrent response test was also carried out to further study their photoelectric properties. Impressively, the responsive photocurrent with intensities of ca.100 and 200 mA mg-1 were surveyed for the MOR and EOR, respectively, demonstrating that the SPR effect from plasmonic Au was beneficial for electrocatalytic oxidation.43 The distinctive core-shell structure and optical properties of the 3D dendritic PtAu@Pt NCs thus offer the possibility of the visible-light-enhanced electrocatalytic applications. In this regard, we herein chose the electrocatalytic oxidation methanol and ethanol to evaluate the catalytic properties of the 3D dendritic PtAu@Pt NCs under the visible light irradiation. The CV operated in 1 M KOH solution (Figure 3a) was a significant mean for evaluating the electrochemically active surface areas (ECSA) of the electrocatalysts, which can provide some crucial information regarding available active sites, and a higher ECSA value means more available surface active 10 ACS Paragon Plus Environment

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sites.44-45 The ECSA value for PtAu1 NCs was calculated to be 15.3 m2 g-1, much superior than that of Pt/C (Figure 3b). The combination of the rough surface and high surface areas may endow such 3D dendritic PtAu@Pt NCs with greatly enhanced surface active sites.46

Figure 3. (a) CV curves of commercial Pt/C, 3D dendritic PtAu1 NCs in the 1 M KOH solution. (b) The ECSA of commercial Pt/C and 3D dendritic PtAu1 NCs. CV curves of commercial Pt/C, 3D dendritic PtAu1 NCs towards (c) MOR and (e) EOR.



(d) The specific and mass activities of commercial Pt/C, 3D dendritic PtAu1 NCs towards (D) MOR and (F) EOR. The electrocatalytic performances were then carried out in 1 M KOH and 1 M CH3OH (CH3CH2OH) solution. As shown in Figure 3c and d, the 3D dendritic PtAu1 NCs exhibited the specific and mass activities of 15.0 mA cm-2 and 2291.4 mA mg-1 towards MOR, which was 5.0 and 9.0 times higher than that of the commercial Pt/C (3.0 mA cm-2 and 254.7 mA mg-1). More importantly, the PtAu1 NCs upon visible light irradiation also achieved a factor of 1.9 times enhancement than those of typical ambient reaction (7.9 mA cm-2 and 1214.4 mA mg-1). The electrocatalytic activities towards EOR (Figure 3e and f) also showed the similar trends to that of MOR. Impressively, the 3D dendritic PtAu1 NCs modified electrode upon the visible light irradiation (37.6 mA cm-2) also had a specific activity of 1.8 and 5.9-fold enhancement than that of the ambient reaction (20.9 mA cm-2) and Pt/C (6.4 mA cm-2), respectively. With regard to the mass activities towards EOR, the PtAu1 NCs under the visible irradiation showed the unprecedentedly high mass activity of 5760.3 mA mg-1, 10.6 and 1.8 times greater than that of Pt/C (545.5 mA mg-1) and the typical ambient reaction (3192.6 mA mg-1), respectively. The electrocatalytic activities of such 3D dendritic PtAu NCs with different compositions have also been studied. As shown in Figure 4a and b, PtAu1.5 and PtAu0.5 showed the ECSA value of 13.1 m2 g-1 and 11.8 m2 g-1. In addition, the PtAu1.5 and PtAu0.5 nanocatalysts have also displayed the greatly enhanced specific activities of 12.7 mA cm-2 (36.3 mA cm-2) and 11.9 mA cm-2 (27.8 mA cm-2) towards MOR 12 ACS Paragon Plus Environment

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(EOR) under visible light irradiation, much higher than those of ambient reaction. Apart from the specific activity, both PtAu1.5 and PtAu0.5 NCs also displayed the greatly enhanced mass activities of 1665.1 mA mg-1 (4623.2 mA mg-1) and 1414.8 mA mg-1 (3283.2 mA mg-1) towards MOR (EOR) when the modified electrodes were upon the visible light irradiation (Figure 4c-f). All of these data have further confirmed that the SPR effects, unique 3D dendritic heterostructure and the synergistic effects between Pt and Au were favorable for the greatly enhanced electrocatalytic activities towards MOR and EOR.47-49



Figure 4. (a) CV curves of 3D dendritic PtAu0.5 NCs and PtAu0.5 NCs in the 1 M KOH solution. (b) The calculated ECSA values of 3D dendritic PtAu0.5 NCs and PtAu0.5 NCs. CV curves of 3D dendritic PtAu0.5 NCs and PtAu0.5 NCs towards (c) MOR and (e) EOR. The specific and mass activities of 3D dendritic PtAu0.5 NCs and PtAu0.5 NCs towards (d) MOR and (f) EOR. The stability of catalyst is a crucial parameter for evaluating the properties of catalysts.50-51 Accordingly, the successive 500 cycles CVs were operated to investigate


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their electrocatalytic durability. As is shown in Figure 5, the peak current densities of these catalysts decayed rapidly in the initial period, while the 3D dendritic PtAu1 NCs upon the visible light irradiation displayed the slowest current decay and retained the highest activity among these catalysts. After 500 cycles, the results showed that the PtAu1 under visible light irradiation retained the catalytic activities of 62 % of the initial value, much higher than that of commercial Pt/C (16 %) and PtAu1 (38 %) modified electrode under ambient reaction, indicating the great enhancement of durability.52



Figure 5. MOR durability comparison of (a and b) 3D dendritic PtAu1 NCs under visible light irradiation, (c and d) 3D dendritic PtAu1 NCs under ambient reaction, and (e and f) commercial Pt/C for the successive CVs of 200th, 300th ,400th and 500th cycles together with the retained specific and mass activities. As for the EOR, the durability variation of these electrocatalysts also displayed the similar trends as MOR (Figure 6), where 3D dendritic PtAu1 NCs upon the visible light irradiation had the highest retained catalytic activities of 65 %, much greater


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than that of the commercial Pt/C (20 %) and the 3D dendritic PtAu1 NCs (42 %) modified electrode under the ambient reaction. These findings imply that such 3D dendritic PtAu@Pt NCs possess more durable and higher catalytic performances towards MOR and EOR, which are also consistent with the above CVs.

Figure 6. EOR durability comparison of (a and b) 3D dendritic PtAu1 NCs under visible light irradiation, (c and d) 3D dendritic PtAu1 NCs under ambient reaction, and (e and f) commercial Pt/C for the successive CVs of 200th, 300th ,400th and 500th



cycles together with the retained specific and mass activities. The electrochemical impedance spectroscopy (EIS) is also a crucial parameter to evaluate the electrical conductivity of samples. From Figure S5, the diameter impedance arc (DIA) of core-shell PtAu@Pt NCs under visible light illumination was much smaller than that under ambient reaction and commercial Pt/C, indicating that PtAu@Pt NCs modified electrode possessed the better electrical conductivity upon visible light illumination.53 Over all, several combined features of the 3D dendritic PtAu@Pt NCs contribute the greatly enhanced performances towards MOR and EOR under visible light irradiation: (1) the unique 3D dendritic structure can provide high surface area available for small organic molecules.

54-55

(2) The strong electronic effects between

Pt and Au may also be significant for the great enhancements of electrocatalytic performances.56-58 (3) Most of all, the SPR-induced transfer is crucial for the substantial promotion of photoelectrocatalytic performances. CONCLUSIONS To summarize, the 3D dendritic core-shell PtAu@Pt NCs have been constructed as advanced visible light catalysts for the electrooxidation of liquid fuel. Compared to the MOR and EOR at the typical ambient condition, more than 1.9 and 1.8 times enhancement in catalytic activity under visible light irradiation have been achieved. The great enhancement in the electrocatalytic activity can be attributed to high exposed surface active areas, efficient adsorption of broad wavelength visible light of the plasmonic Au, and efficient electron transfers between Pt and Au. Such excellent 18 ACS Paragon Plus Environment

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features exhibit the superiority of core-shell PtAu@Pt NCs as high-performance photocatalysts towards liquid fuel oxidation. It is believed that the tremendous efforts in this work may pave up new route for engineering efficient visible-light-driven plasmonic photocatalysts with potential applications for the photoelectrocatalytic liquid fuel oxidation reaction. ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website. TEM images of the as-prepared samples. EIS experiments for the commercial Pt/C, PtAu1 NCs modified electrode under visible light irradiation and under ambient reaction towards EOR. AUTHOR INFORMATION Corresponding Author E-mail: [email protected] (Y.D.); [email protected]. Tel: +86-512-65880089, Fax: +86-512-65880089 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (Grant No. 51373111), the Suzhou Industry (SYG201636), the project of scientific and 19 ACS Paragon Plus Environment


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technologic infrastructure of Suzhou (SZS201708), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

REFERENCES 1.

Shi, R.; Cao, Y.; Bao, Y.; Zhao, Y.; Waterhouse, G. I. N.; Fang, Z.; Wu, L. Z.; Tung, C. H.; Yin, Y.;

Zhang, T., Self-assembled Au/CdSe nanocrystal clusters for plasmon-mediated photocatalytic hydrogen evolution. Adv. Mater. 2017, 29. DOI: 10.1002/adma.201700803 2.

Fei, J.; Li, J., Controlled preparation of porous TiO2-Ag nanostructures through supramolecular

assembly

for

plasmon-enhanced

photocatalysis.

Adv.

Mater.

2015,

27,

314-319.

DOI:

10.1002/adma.201404007 3.

Choi, K. M.; Kim, D.; Rungtaweevoranit, B.; Trickett, C. A.; Barmanbek, J. T.; Alshammari, A. S.;

Yang, P.; Yaghi, O. M., Plasmon-enhanced photocatalytic CO(2) conversion within metal-organic frameworks under visible light. J. Am. Chem. Soc. 2017, 139, 356-362. DOI: 10.1021/jacs.6b11027 4.

Wu, B.; Liu, D.; Mubeen, S.; Chuong, T. T.; Moskovits, M.; Stucky, G. D., Anisotropic growth of

TiO2 onto gold nanorods for plasmon-enhanced hydrogen production from water reduction. J. Am. Chem. Soc. 2016, 138, 1114-1117. DOI: 10.1021/jacs.5b11341 5.

Liu, S.; Jiang, R.; You, P.; Zhu, X.; Wang, J.; Yan, F., Au/Ag core–shell nanocuboids for

high-efficiency organic solar cells with broadband plasmonic enhancement. Energy Environ. Sci. 2016, 9, 898-905. DOI: 10.1039/C5EE03779D 6.

Wang, F.; Li, C.; Chen, H.; Jiang, R.; Sun, L. D.; Li, Q.; Wang, J.; Yu, J. C.; Yan, C. H., Plasmonic

harvesting of light energy for suzuki coupling reactions. J. Am. Chem. Soc. 2013, 135, 5588-5601. DOI: 10.1021/ja310501y 7.

Jiang, R.; Li, B.; Fang, C.; Wang, J., Metal/Semiconductor hybrid nanostructures for


Page 21 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


plasmon-enhanced applications. Adv. Mater. 2014, 26, 5274-5309. DOI: 10.1002/adma.201400203 8.

Wu, B.-H.; Liu, W.-T.; Chen, T.-Y.; Perng, T.-P.; Huang, J.-H.; Chen, L.-J., Plasmon-enhanced

photocatalytic hydrogen production on Au/TiO2 hybrid nanocrystal arrays. Nano Energy 2016, 27, 412-419. DOI: 10.1016/j.nanoen.2016.07.029 9.

Zheng, Z.; Tachikawa, T.; Majima, T., Plasmon-enhanced formic acid dehydrogenation using

anisotropic Pd-Au nanorods studied at the single-particle level. J. Am. Chem. Soc. 2015, 137, 948-957. DOI: 10.1021/ja511719g 10. Jang, S.; Kang, J. S.; Lee, J.-K.; Kim, S. M.; Son, Y. J.; Lim, A.; Cho, H.; Kim, J.; Jeong, J.; Lee, G.; Sung, Y.-E.; Choi, M., Enhanced light harvesting in mesoscopic solar cells by multilevel multiscale patterned photoelectrodes with superpositioned optical properties. Adv. Funct. Mater. 2016, 26, 6584-6592. DOI: 10.1002/adfm.201601586 11. Lou, Z.; Kim, S.; Zhang, P.; Shi, X.; Fujitsuka, M.; Majima, T., In situ observation of single Au triangular nanoprism etching to various shapes for plasmonic photocatalytic hydrogen Generation. ACS nano 2017, 11, 968-974. DOI: 10.1021/acsnano.6b07581 12. Hou, W.; Cronin, S. B., A review of surface plasmon resonance-enhanced photocatalysis. Adv. Funct. Mater. 2013, 23, 1612-1619. DOI: 10.1002/adfm.201202148 13. Bai, S.; Li, X.; Kong, Q.; Long, R.; Wang, C.; Jiang, J.; Xiong, Y., Toward enhanced photocatalytic oxygen evolution: synergetic utilization of plasmonic effect and schottky junction via interfacing facet selection. Adv. Mater. 2015, 27, 3444-3452. DOI: 10.1002/adma.201501200 14. Choi, Y.; Hong, S.; Liu, L.; Kim, S. K.; Park, S., Galvanically replaced hollow Au-Ag nanospheres: study of their surface plasmon resonance. Langmuir 2012, 28, 6670-6676. DOI: 10.1021/la202569q



Page 22 of 29

15. Lee, Y. K.; Ahn, K.; Cha, J.; Zhou, C.; Kim, H. S.; Choi, G.; Chae, S. I.; Park, J. H.; Cho, S. P.; Park, S. H.; Sung, Y. E.; Lee, W. B.; Hyeon, T.; Chung, I., Enhancing p-type thermoelectric performances of polycrystalline SnSe via tuning phase transition temperature. J. Am. Chem. Soc. 2017, 139, 10887-10896. DOI: 10.1021/jacs.7b05881 16. Yang, H.; He, L. Q.; Hu, Y. W.; Lu, X.; Li, G. R.; Liu, B.; Ren, B.; Tong, Y.; Fang, P. P., Quantitative detection of photothermal and photoelectrocatalytic effects induced by SPR from Au@Pt Nanoparticles. Angew. Chem. 2015, 54, 11462-11466. DOI: 10.1002/ange.201505985 17. Lou, Z.; Fujitsuka, M.; Majima, T., Two-Dimensional Au-nanoprism/reduced graphene oxide/Pt-nanoframe as plasmonic photocatalysts with multiplasmon modes boosting hot electron transfer

for

hydrogen

generation.

J.

Phys.

Chem.

Lett.

2017,

8,

844-849.

DOI:

10.1021/acs.jpclett.6b03045 18. Xue, J.; Ma, S.; Zhou, Y.; Zhang, Z.; He, M., Facile photochemical synthesis of Au/Pt/g-C3N4 with plasmon-enhanced photocatalytic activity for antibiotic pegradation. ACS Appl. Mater. Interfaces 2015, 7, 9630-967. DOI: 10.1021/acsami.5b01212 19. Erwin, W. R.; Coppola, A.; Zarick, H. F.; Arora, P.; Miller, K. J.; Bardhan, R., Plasmon enhanced water splitting mediated by hybrid bimetallic Au-Ag core-shell nanostructures. Nanoscale 2014, 6, 12626-12634. DOI: 10.1039/C4NR03625E 20. Xu, H.; Yan, B.; Wang, J.; Zhang, K.; Li, S.; Xiong, Z.; Wang, C.; Shiraishi, Y.; Du, Y.; Yang, P., Self-supported porous 2D AuCu triangular nanoprisms as model electrocatalysts for ethylene glycol and glycerol oxidation. J. Mater. Chem. A 2017, 5, 15932-15939. DOI: 10.1039/C7TA04598K 21. Ding, S. J.; Yang, D. J.; Li, J. L.; Pan, G. M.; Ma, L.; Lin, Y. J.; Wang, J. H.; Zhou, L.; Feng, M.; Xu, H.; Gao, S.; Wang, Q. Q., The nonmonotonous shift of quantum plasmon resonance and


Page 23 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


plasmon-enhanced photocatalytic activity of gold nanoparticles. Nanoscale 2017, 9, 3188-3195. DOI: 10.1039/C6NR08962C 22. Kamimura, S.; Miyazaki, T.; Zhang, M.; Li, Y.; Tsubota, T.; Ohno, T., (Au@Ag)@Au double shell nanoparticles loaded on rutile TiO2 for photocatalytic decomposition of 2-propanol under visible light irradiation. Appl. Catal. B Environ. 2016, 180, 255-262. DOI: 10.1016/j.apcatb.2015.06.037 23. Kamimura, S.; Yamashita, S.; Abe, S.; Tsubota, T.; Ohno, T., Effect of core@shell (Au@Ag) nanostructure on surface plasmon-induced photocatalytic activity under visible light irradiation. Appl. Catal. B Environ. 2017, 211, 11-17. DOI: 10.1016/j.apcatb.2017.04.028 24. Wei, R.-B.; Kuang, P,-Y.; Cheng, H., Chen, Y,-B.; Long, J,-Y.; Zhang, M,-Y.; Liu, Z,-Q., Plasmon-enhanced photoelectrochemical water splitting on gold nanoparticle decorated ZnO/CdS nanotube

arrays.

ACS

Sustainable

Chem.

Eng.

2017,

5,

4249-4257.

DOI:

10.1021/acssuschemeng.7b00242 25. Xu, H.; Wang, J.; Yan, B.; Zhang, K.; Li, S.; Wang, C.; Shiraishi, Y.; Du, Y.; Yang, P., Hollow AuxAg/Au core/shell nanospheres as efficient catalysts for electrooxidation of liquid fuels. Nanoscale 2017, 9, 12996-13003. DOI: 10.1039/C7NR04409G 26. Ataee-Esfahani, H.; Wang, L.; Nemoto, Y.; Yamauchi, Y., Synthesis of bimetallic Au@Pt nanoparticles with Au core and nanostructured Pt shell toward highly active electrocatalysts. Chem. Mater. 2010, 22, 6310-6318. DOI: 10.1021/cm102074w 27. Wang, L.; Yamauchi, Y., Strategic synthesis of trimetallic Au@Pd@Pt core-shell nanoparticles from poly(vinylpyrrolidone)-based aqueous solution toward highly active electrocatalysts. Chem. Mater. 2011, 23, 2457-2465. DOI: 10.1021/cm200382s 28. Oko, D. N.; Zhang, J.; Garbarino, S.; Chaker, M.; Ma, D.; Tavares, A. C.; Guay, D., Formic acid



Page 24 of 29

electro-oxidation at PtAu alloyed nanoparticles synthesized by pulsed laser ablation in liquids. J. Power Sources 2014, 248, 273-282. DOI: 10.1016/j.jpowsour.2013.09.045 29. Tan, T.; Xie, H.; Xie, J.; Ping, H.; Su, B.-L.; Wang, W.; Wang, H.; Munir, Z. A.; Fu, Z., Photo-assisted synthesis of Au@PtAu core–shell nanoparticles with controllable surface composition for methanol electro-oxidation. J. Mater. Chem. A 2016, 4, 18983-18989. DOI: 10.1039/C6TA07314J 30. Shao, F.-Q.; Lin, X.-X.; Feng, J.-J.; Yuan, J.; Chen, J.-R.; Wang, A.-J., Simple fabrication of core-shell AuPt@Pt nanocrystals supported on reduced graphene oxide for ethylene glycol oxidation and

hydrogen

evolution

reactions.

Electrochim.

Acta

2016,

219,

321-329.

DOI:

10.1016/j.electacta.2016.09.158 31. Liu, Q.; Xu, Y.-R.; Wang, A.-J.; Feng, J.-J., Simple wet-chemical synthesis of core–shell Au– Pd@Pd nanocrystals and their improved electrocatalytic activity for ethylene glycol oxidation reaction. Int. J. Hydrogen Energy 2016, 41, 2547-2553. DOI: 10.1016/j.ijhydene.2015.11.143 32. Yu, D.-X.; Wang, A.-J.; He, L.-L.; Yuan, J.; Wu, L.; Chen, J.-R.; Feng, J.-J., Facile synthesis of uniform AuPd@Pd nanocrystals supported on three-dimensional porous N-doped reduced graphene oxide hydrogels as highly active catalyst for methanol oxidation reaction. Electrochim. Acta 2016, 213, 565-573. DOI: 10.1016/j.electacta.2016.07.141 33. Xu, H.; Zhang, K.; Yan, B.; Wang, J.; Wang, C.; Li, S.; Gu, Z.; Du, Y.; Yang, P., Ultra-uniform PdBi nanodots with high activity towards formic acid oxidation. J. Power Sources 2017, 356, 27-35. DOI: 10.1016/j.jpowsour.2017.04.070 34. Xu, H.; Yan, B.; Zhang, K.; Wang, J.; Li, S.; Wang, C.; Shiraishi, Y.; Du, Y.; Yang, P., Ultrasonic-assisted synthesis of N-doped graphene-supported binary PdAu nanoflowers for enhanced electro-oxidation of ethylene glycol and glycerol. Electrochim. Acta 2017, 245, 227-236. DOI:


Page 25 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


10.1016/j.electacta.2017.05.146 35. Jiang, X.; Yan, X.; Ren, W.; Jia, Y.; Chen, J.; Sun, D.; Xu, L.; Tang, Y., Porous AgPt@Pt nanooctahedra as an Efficient Catalyst toward formic acid oxidation with predominant dehydrogenation

pathway.

ACS

Appl.

Mater.

Interfaces

2016,

8,

31076-31082.

DOI:

10.1021/acsami.6b11895 36. Chang, J.; Feng, L.; Jiang, K.; Xue, H.; Cai, W.-B.; Liu, C.; Xing, W., Pt–CoP/C as an alternative PtRu/C catalyst for direct methanol fuel cells. J. Mater. Chem. A 2016, 4, 18607-18613. DOI: 10.1039/C6TA07896F 37. Huang, D. B.; Yuan, Q.; He, P. L.; Wang, K.; Wang, X., A facile and general strategy for the synthesis of porous flowerlike Pt-based nanocrystals as effective electrocatalysts for alcohol oxidation. Nanoscale 2016, 8, 14705-14710. DOI: 10.1039/C6NR04927C 38. Sun, X.; Li, D.; Guo, S.; Zhu, W.; Sun, S., Controlling core/shell Au/FePt nanoparticle electrocatalysis via changing the core size and shell thickness. Nanoscale 2016, 8, 2626-2631. DOI: 10.1039/C5NR06492A 39. Wang, W.; Yan, Y.; Zhou, N.; Zhang, H.; Li, D.; Yang, D., Seed-mediated growth of Au nanorings with size control on Pd ultrathin nanosheets and their tunable surface plasmonic properties. Nanoscale 2016, 8, 3704-3710. DOI: 10.1039/C5NR08613B 40. Zhai, Y.; DuChene, J. S.; Wang, Y. C.; Qiu, J.; Johnston-Peck, A. C.; You, B.; Guo, W.; DiCiaccio, B.; Qian, K.; Zhao, E. W.; Ooi, F.; Hu, D.; Su, D.; Stach, E. A.; Zhu, Z.; Wei, W. D., Polyvinylpyrrolidone-induced anisotropic growth of gold nanoprisms in plasmon-driven synthesis. Nature Mater. 2016, 15, 889-895. DOI: 10.1038/nmat4683 41. Zhang, Z.; Li, A.; Cao, S. W.; Bosman, M.; Li, S.; Xue, C., Direct evidence of plasmon



enhancement on photocatalytic hydrogen generation over Au/Pt-decorated TiO2 nanofibers. Nanoscale 2014, 6, 5217-22. DOI: 10.1039/C3NR06562F 42. Yang, H.; He, L.-Q.; Wang, Z.-H.; Zheng, Y.-Y.; Lu, X.; Li, G.-R.; Fang, P.-P.; Chen, J.; Tong, Y., Surface plasmon resonance promoted photoelectrocatalyst by visible light from Au core Pd shell Pt cluster nanoparticles. Electrochim. Acta 2016, 209, 591-598. DOI: 10.1016/j.electacta.2016.05.120 43. Huang, J.; Zhu, Y.; Liu, C.; Zhao, Y.; Liu, Z.; Hedhili, M. N.; Fratalocchi, A.; Han, Y., Fabricating a homogeneously alloyed AuAg shell on Au nanorods to achieve strong, stable, and tunable surface plasmon resonances. Small 2015, 11, 5214-5221. DOI: 10.1002/smll.201501220 44. Xu, H.; Yan, B.; Zhang, K.; Wang, C.; Zhong, J.; Li, S.; Yang, P.; Du, Y., Facile synthesis of Pd-Ru-P ternary nanoparticle networks with enhanced electrocatalytic performance for methanol oxidation. Int. J. Hydrogen Energy 2017, 42, 11229-11238. DOI: 10.1016/j.ijhydene.2017.03.023 45. Xu, H.; Yan, B.; Zhang, K.; Wang, J.; Li, S.; Wang, C.; Shiraishi, Y.; Du, Y.; Yang, P., Facile fabrication of novel PdRu nanoflowers as highly active catalysts for the electrooxidation of methanol. J. Colloid Interface Sci. 2017, 505, 1-8. DOI: 10.1016/j.jcis.2017.05.067 46. Kannan, R.; Kim, A. R.; Nahm, K. S.; Yoo, D. J., One-pot synthesis and electrocatalytic performance of Pd/MnOx/graphene nanocomposite for electrooxidation of ethylene glycol. Int. J. Hydrogen Energy 2015, 40, 11960-11967. DOI: 10.1016/j.ijhydene.2015.06.032 47. Tsao, Y. C.; Rej, S.; Chiu, C. Y.; Huang, M. H., Aqueous phase synthesis of Au-Ag core-shell nanocrystals with tunable shapes and their optical and catalytic properties. J. Am. Chem. Soc. 2014, 136, 396-404. DOI: 10.1021/ja410663g 48. Hu, S.; Munoz, F.; Noborikawa, J.; Haan, J.; Scudiero, L.; Ha, S., Carbon supported Pd-based bimetallic and trimetallic catalyst for formic acid electrochemical oxidation. Appl. Catal. B Environ.


Page 26 of 29

Page 27 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2016, 180, 758-765. DOI: 10.1016/j.apcatb.2015.07.023 49. Kannan, R.; Kim, A. R.; Nahm, K. S.; Lee, H. K.; Yoo, D. J., Synchronized synthesis of Pd@C-RGO carbocatalyst for improved anode and cathode performance for direct ethylene glycol fuel cell. Chem. Commun. 2014, 50, 14623-14626. DOI: 10.1039/C4CC06879C 50. Xu, H.; Wang, J.; Yan, B.; Li, S.; Wang, C.; Shiraishi, Y.; Yang, P.; Du, Y., Facile construction of fascinating trimetallic PdAuAg nanocages with exceptional ethylene glycol and glycerol oxidation activity. Nanoscale 2017, 9, 17004-17012. DOI: 10.1039/C7NR06737B 51. Xu, H.; Yan, B.; Zhang, K.; Wang, J.; Li, S.; Wang, C.; Shiraishi, Y.; Du, Y.; Yang, P., Synthesis and characterization of core-shell PdAu convex nanospheres with enhanced electrocatalytic activity for ethylene glycol oxidation. J. Alloys Compnds. 2017, 723, 36-42. DOI: 10.1016/j.jallcom.2017.06.230 52. Chen, Q.; Cao, Z.; Du, G.; Kuang, Q.; Huang, J.; Xie, Z.; Zheng, L., Excavated octahedral Pt-Co alloy nanocrystals built with ultrathin nanosheets as superior multifunctional electrocatalysts for energy conversion applications. Nano Energy 2017, 39, 582-589. DOI: 10.1016/j.nanoen.2017.07.041 53. Xu, H.; Yan, B.; Zhang, K.; Wang, C.; Zhong, J.; Li, S.; Du, Y.; Yang, P., PVP-stabilized PdAu nanowire networks prepared in different solvents endowed with high electrocatalytic activities for the oxidation of ethylene glycol and isopropanol. Colloids Surf., A 2017, 522, 335-345. DOI: 10.1016/j.colsurfa.2017.03.015 54. Ataee-Esfahani, H.; Imura, M.; Yamauchi, Y., All-metal mesoporous nanocolloids: solution-phase synthesis of core-shell Pd@Pt nanoparticles with a designed concave surface. Angew. Chem. 2013, 52, 13611-13615. DOI: 10.1002/anie.201307126 55. Liu, H.; Qu, J.; Chen, Y.; Li, J.; Ye, F.; Lee, J. Y.; Yang, J., Hollow and cage-bell structured nanomaterials of noble metals. J. Am. Chem. Soc. 2012, 134, 11602-11610. DOI: 10.1021/ja407773x



Page 28 of 29

56. Wang, L.; Yamauchi, Y., Metallic nanocages: synthesis of bimetallic Pt-Pd hollow nanoparticles with dendritic shells by selective chemical etching. J. Am. Chem. Soc. 2013, 135, 16762-16765. 57.

Xu, H.; Yan, B.; Li, S.; Wang, J.; Wang, C.; Guo, J.; Du, Y., N-doped graphene supported PtAu/Pt

intermetallic core/dendritic shell nanocrystals for efficient electrocatalytic oxidation of formic acid. Chem. Eng. J.1 2018, 334, 2638-2646. DOI: 10.1016/j.cej.2017.10.175 58. Malgras, V.; Ataee-Esfahani, H.; Wang, H.; Jiang, B.; Li, C.; Wu, K. C.; Kim, J. H.; Yamauchi, Y., nanoarchitectures

for

mesoporous

metals.

Adv.

Mater.

10.1002/adma.201502593


2016,

28,

993-1010.

DOI:

Page 29 of 29 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For Table of Content Use Only The 3D dendritic core-shell PtAu@Pt NCs have been constructed as advanced visible-light-driven catalysts for the electrooxidation of liquid fuel.


Visible-Light-Driven 3D Dendritic PtAu@Pt Core-Shell Photocatalyst

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