Synthesis of Palladium Right Bipyramids with a Singly Twinned Structure†

doi:10.7503/cjcu20170337

Abstract

Abstract:

Through solution phase reduction route, palladium right bipyramid nanocrystals with a singly twinned structure were synthesized with Na₂PdCl₄ as a precursor, PVP as a stabilizer and reductant, I^- as a plane-selective capping agent and coordination reagent, and N $O 3 -$ as an etching agent in a hydrophilic system. When n(Na₂PdCl₄)∶n(PVP)∶n(KI)∶n(NaNO₃)=1∶35∶10∶9 and pH=11, well-defined palladium right bipyramid nanocrystals with purity higher than 99% could be achieved. I^- in the present reaction system affected the growth and transformation of crystal seed and the morphology of final product by changing reduction rate of Pd precursor, whereas the effect of I^- on oxidative etching was not obvious at high pH value. The ratio of K⁺/Na⁺ considerably influenced the morphology of product, showing a cation effect, which was possibly attributed to higher reduction rate in the presence of Na⁺ than that in the presence of K⁺.

Key words: Right triangular bipyramid, Singly twinned Pd nanocrystal, Oxidative etching, Reduction rate, Cation effect

CLC Number:

O614
O641

TrendMD:

SUN Changyong, LIN Liangbiao, XIE Xiaowei. Synthesis of Palladium Right Bipyramids with a Singly Twinned Structure^†[J]. Chem. J. Chinese Universities, 2017, 38(12): 2149.

Figures/Tables 8

Fig.1 TEM images of as-synthesized sample at low and high magnificationsn(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶20∶8, initial pH=11. The inset of (C) shows 3D models of individual Pd right bipyramids in three common orientations that correspond to the different projected shapes, yellow denotes {111} twin plane inside the crystal, all exposed facets are {100} without coloring.

Fig.2 HRTEM images of Pd right bipyramid(A) and 5-fold twinned wire(B) with 3D models showing e-beam orientations and the corresponding FT pictures(insets)

Fig.3 TEM images of the as-synthesized samples at initial pH of 9(A, B) and 7(C, D)n(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶20∶8.

Fig.4 TEM images of the as-synthesized samples under different NaNO3 dosagesn(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶20∶X. (A), (B) X=0; (C), (D) X=4; (E), (F) X=10.

Fig.5 TEM images of the as-synthesized samples under different KI dosagesn(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶X∶8. (A), (B) X=10; (C), (D) X=30.

Fig.6 TEM images of the as-synthesized sample under optimal conditionsn(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶10∶9.

Fig.7 TEM images of the as-synthesized sample using NaI instead of KIn(Na2PdCl4)∶n(PVP)∶n(NaI)∶n(NaNO3)=1∶35∶20∶0.

Fig.8 UV-Vis spectra at different reaction stages(A) n(Na2PdCl4)∶n(PVP)∶n(KI)∶n(NaNO3)=1∶35∶20∶0; (B) n(Na2PdCl4)∶n(PVP)∶n(NaI)∶n(NaNO3)=1∶35∶20∶0. The inset depicts the time dependence of the absorbance around 343 nm, which is directly proportional to the concentration of the [PdI4]2- species.

References 25

[1]	Burda C., Chen X. B., Narayanan R., El-Sayed M. A., Chem. Rev., 2005, 105(4), 1025—1102
[2]	Xia Y., Xiong Y., Lim B., Skrabalak S. E., Angew. Chem. Int. Ed., 2009, 48(1), 60—103
[3]	Nishihata Y., Mizuki J., Akao T., Tanaka H., Uenishi M., Kimura M., Okamoto T., Hamada N., Nature,2002, 418(6894), 164—167
[4]	Yin L. X., Liebscher J., Chem. Rev., 2007, 107(1), 133—173
[5]	Zhang H., Jin M. S., Xiong Y. J., Lim B., Xia Y. N., Accounts Chem. Res., 2013, 46(8), 1783—1794
[6]	Zhou W., Wu J. B., Yang H., Nano Letters, 2013, 13(6), 2870—2874
[7]	Cheong S. S., Watt J. D., Tilley R. D., Nanoscale,2010, 2(10), 2045—2053
[8]	Zhan C., Cheng R., Fang B., Zhao L., Chem. Res. Chinese Universities, 2016, 32(2), 159—164
[9]	Chai Z. Z., Zheng W. J., Chem. J. Chinese Universities, 2016, 37(3), 435—441
	( 柴臻臻, 郑文君. 高等学校化学学报, 2016, 37(3 ), 435—441)
[10]	Lim B., Xiong Y., Xia Y., Angew. Chem. Int. Ed., 2007, 46(48), 9279—9282
[11]	Xiong Y., McLellan J. M., Yin Y., Xia Y., Angew. Chem. Int. Ed., 2007, 46(5), 790—794
[12]	Li C., Sato R., Kanehara M., Zeng H., Bando Y., Teranishi T., Angew. Chem. Int. Ed., 2009, 121(37), 7015—7019
[13]	Huang H. W., Wang Y., Ruditskiy A., Peng H. C., Zhao X., Zhang L., Liu J. Y., Ye Z. Z., Xia Y. N., ACS Nano, 2014, 8(7), 7041—7050
[14]	Huang X., Zheng N., J. Am. Chem. Soc., 2009, 131(13), 4602—4603
[15]	Lu N., Chen W., Fang G. Y., Chen B., Yang K. Q., Yang Y., Wang Z. C., Huang S. M., Li Y. D., Chem. Mater., 2014, 26(7), 2453—2459
[16]	Xiong Y. J., McLellan J. M., Chen J. Y., Yin Y. D., Li Z. Y., Xia Y. N., J. Am. Chem. Soc., 2005, 127(48), 17118—17127
[17]	Xia X. H., Choi S. I., Herron J. A., Lu N., Scaranto J., Peng H. C., Wang J. G., Mavrikakis M., Kim M. J., Xia Y. N., J. Am. Chem. Soc., 2013, 135(42), 15706—15709
[18]	Xiong Y., Chen J., Wiley B., Xia Y., Yin Y., Li Z. Y., Nano Letters, 2005, 5(7), 1237—1242
[19]	Niu W. X., Li Z. Y., Shi L. H., Liu X. Q., Li H. J., Han S., Chen J., Xu G. B., Crystal Growth & Design, 2008, 8(12), 4440—4444
[20]	Niu W., Zhang L., Xu G., ACS Nano, 2010, 4(4), 1987—1996
[21]	Zhang J. F., Feng C., Deng Y. D., Liu L., Wu Y. T., Shen B., Zhong C., Hu W. B., Chem. Mater., 2014, 26(2), 1213—1218
[22]	Zheng Y., Zeng J., Ruditskiy A., Liu M., Xia Y., Chem. Mater., 2014, 26(1), 22—33
[23]	Choi S. I., Herron J. A., Scaranto J., Huang H., Wang Y., Xia X., Lv T., Park J., Peng H. C., Mavrikakis M., Xia Y., Chem. Cat. Chem., 2015, 7(14), 2077—2084
[24]	Wang C. M., Wang L. L., Long R., Ma L., Wang L. M., Li Z. Q., Xiong Y. J., J. Mater. Chem., 2012, 22(17), 8195—8198
[25]	Xiong Y. J., Xia Y. N., Adv. Mater., 2007, 19(20), 3385—3391