三维多孔核壳结构PdNi@Au催化剂的制备及对甲酸的电催化氧化

doi:10.7503/cjcu20180776

摘要/Abstract

摘要：

以K₂PdCl₄/K₂Ni(CN)₄为前驱体制备了具有凝胶特性的氰胶(Cyanogels), 利用硼氢化钠还原氰胶得到三维多孔珊瑚状PdNi合金前驱体, 在此基础上通过原位Galvanic置换反应, 制备得到内核为PdNi合金、表面具有不同厚度Au层的三维多孔PdNi@Au催化剂. X射线衍射(XRD)分析和透射电子显微镜(TEM)观测结果显示, 该三维网状结构由粒径约7 nm的纳米颗粒相互连接形成; 能量分散光谱(EDX)线性扫描和元素分布(Mapping)分析显示该催化剂具有典型的核壳结构. 电化学测试结果表明, 表面Au层的厚度影响PdNi@Au催化剂的性能, 当Au的含量(摩尔分数)为5.6%时, 催化剂显示出对甲酸最佳的电催化活性, 对甲酸电催化氧化的峰电流密度达到商业化铂黑催化剂的7.2倍.

关键词: 钯基催化剂, Galvanic置换反应, 甲酸电催化氧化

Abstract:

K₂PdCl₄ and K₂Ni(CN)₄ were employed as precursors to fabricate cyanogel, which was then reduced by NaBH₄ to prepare 3D porous coral-like PdNi alloy. On the basis of the synthesized PdNi alloy, 3D porous PdNi@Au catalysts with PdNi alloy as inner core and Au layers of different thickness on the surface were synthesized by in situ Galvanic replacement between PdNi alloy and HAuCl₄ aqueous solution. X-Ray diffraction(XRD) and transmission electron microscopy(TEM) indicated that the 3D network structure was composed of interconnected nanoparticles with diameter of 7 nm. Energy dispersive X-ray(EDX) line scanning and mapping could declare its typical core-shell structure. Electrochemical measurements demonstrated that the electro-catalytic performance of PdNi@Au catalysts could be affected by the thickness of Au layer. When the content of Au reached a value of 5.6%(molar fraction), PdNi@Au catalyst exhibited the best catalytic performance for formic acid electro-oxidation. In this case, the peak current density of PdNi@Au catalyst was 7.2 times that of commercial Pd black.

Key words: Pd-based catalyst, Galvanic replacement, Formic acid electro-oxidation

中图分类号:

O646

TrendMD:

李家辉, 秦梦寒, 张洁, 杜仪, 孙冬梅, 唐亚文. 三维多孔核壳结构PdNi@Au催化剂的制备及对甲酸的电催化氧化. 高等学校化学学报, 2019, 40(5): 988.

LI Jiahui,QIN Menghan,ZHANG Jie,DU Yi,SUN Dongmei,TANG Yawen. Fabrication of 3D Porous Core-shell PdNi@Au Nanocatalyst for Formic Acid Electro-oxidation^†. Chem. J. Chinese Universities, 2019, 40(5): 988.

图/表 11

Scheme 1 Synthetic routes of PdNi@Au catalyst(A) Orange jelly-like PdNi cyanogel and its ball-stick model; (B) photograph of 3D porous PdNi alloy with network structure; (C) schematic diagram of PdNi@Au catalyst.

Fig.1 UV spectroscopy of reaction system at different time

Fig.2 EDX pattern of PdNi@Au-5.6 catalyst(B)

Fig.3 Typical SEM(A), TEM(B) and HRTEM(C) images of PdNi@Au-5.6 catalyst The insets in (B) and (C) are corresponding SAED pattern and the outer Au layer, respectively.

Fig.4 EDX line scanning pattern of PdNi@Au-5.6 catalystInset is corresponding HRTEM image of the EDX line scanning test region.

Fig.5 HAADF-STEM image(A) and EDX mapping patterns of PdNi@Au-5.6 catalyst(B—E) (B) Ni; (C) Pd; (D) Au; (E) overlap.

Fig.6 XRD patterns of different catalysts

Fig.7 XPS spectra of PdNi@Au-5.6(A) Full scan; (B) Pd3d region; (D) Au4f region.

Fig.8 CV curves of different catalysts in N2-saturated 0.5 mol/L H2SO4(A) and in N2-saturated 0.5 mol/L H2SO4+0.1 mol/L HCOOH(B)Inset in (B) is corresponding Tafel plots.

Fig.9 Chronoamperometry curves at 0 V for 3000 s in N2-saturated 0.5 mol/L H2SO4+0.1 mol/L HCOOH(A) and CO-stripping voltammograms in N2-saturated 0.5 mol/L H2SO4(B) of different catalysts

Fig.10 CV curves of different catalysts in N2-saturated 0.5 mol/L H2SO4+ 0.1 mol/L HCOOH solution(A) and histogram of mass-normalized peak current for different catalysts(B)a. PdNi@Au-2.8; b. PdNi@Au-5.6; c. PdNi@Au-11.2; d. PdNi@Au-16.8.

参考文献 35

[1]	Au L., Chen Y., Zhou F., Camargo P. H. C., Lim B., Li Z. Y., Ginger D. S., Xia Y. N., Nano Res., 2008, 1(6), 441—449
[2]	Jiang T. T., Song J. L. Q., Zhang W. T., Wang H., Li X. D., Xia R. X., Zhu L. X., Xu X. L., ACS Appl. Mater. Interfaces,2015, 7(39), 21985—21994
[3]	Liu Z. Y., Fu G. T., Tang Y. W., Sun D. M., Chen Y., Lu T. H., Cryst. Eng. Comm.,2014, 16(36), 8576—8581
[4]	Geetha B. R., Muthoosamy K., Zhou M. F., Ashokkumar M., Huang N. M., Manickam S., Biosens. Bioelectron.,2017, 87, 622—629
[5]	Wu H. X., Wang P., He H. L., Jin Y. D., Nano Res., 2012, 5(2), 135—144
[6]	Liu X. L., Liang S., Nan F., Yang Z. J., Yu X. F., Zhou L., Hao Z. H., Wang Q. Q., Nanoscale,2013, 5(12), 5368—5374
[7]	Lang X.Y., Yuan H. T., Iwasa Y., Chen M. W.,Scr. Mater., 2011, 64(9), 923—926
[8]	Jiang X., Qiu X. Y., Fu G. T., Sun J. Z., Huang Z. N., Sun D. M., Xu L., Zhou J. C., Tang Y. W., J. Mater. Chem. A,2018, 6(36), 17682—17687
[9]	Zhu W. L., Zhang Y. J., Zhang H. Y., Lv H. F., Li Q., Michalsky R., Peterson A. A., Sun S. H., J. Am. Chem. Soc.,2014, 136(46), 16132—16135
[10]	Ye X. C., Gao Y. Z., Chen J., Reifsnyder D. C., Zheng C., Murray C. B., Nano Lett., 2013, 13(5), 2163—2171
[11]	Garg N., Scholl C., Mohanty A., Jin R. C., Langmuir,2010, 26(12), 10271—10276
[12]	Li Y. Q., Zhu Q., Xiao Z. L., Lv C. Z., Feng Z. M., Yin Y. L., Cao Z., Chem. J. Chinese Universities,2018, 39(4), 636—644
	(李雨晴, 朱钦, 肖忠良, 吕超志, 冯泽猛, 印遇龙, 曹忠. 高等学校化学学报,2018, 39(4), 636—644)
[13]	Zhao N. N., Wei Y., Sun N. J., Chen Q., Bai J. W., Zhou L. P., Qin Y., Li M. X., Qi L. M., Langmuir,2008, 24(3), 991—998
[14]	Zhang R. Y., Hummelgard M., Olin H., PLoS One,2012, 7(1), e30469
[15]	Hu J., Gan Q. M., Zhang Y. L., Ren B., Li Y. J., Mater. Chem. Phys.,2015, 163, 529—536
[16]	Xie J. P., Zhang Q. B., Lee J. Y., Wang D. I. C., ACS Nano,2008, 2(12), 2473—2480
[17]	Li S. N., Zhang L. Y., Wang T. T., Li L., Wang C. G., Su Z. M., Chem. Commun.,2015, 51(76), 14338—14341
[18]	Lee K. Y., Kim M., Noh J. S., Choi H. C., Lee W., J. Mater. Chem. A,2013, 1(44), 13890—13895
[19]	Wang L., Imura M., Yamauchi Y., Cryst. Eng. Comm.,2012, 14(22), 7594—7599
[20]	Ke X., Li Z. H., Gan L., Zhao J., Cui G. F., Kellogg W., Matera D., Higgins D., Wu G., Electrochim. Acta,2015, 170, 337—342
[21]	Ke X., Xu Y. T., Yu C. C., Zhao J., Cui G. F., Higgins D., Chen Z. W., Li Q., Xu H., Wu G., J. Mater. Chem. A,2014, 2(39), 16474—16479
[22]	Zhong S. L., Zhuang J. Y., Yang D. P., Tang D. P., Biosens. Bioelectron., 2017, 96, 26—32
[23]	Ke X., Xu Y. T., Yu C. C., Zhao J., Cui G. F., Higgins D., Li Q., Wu G., J. Power Sources,2014, 269, 461—465
[24]	El-Said W. A., Lee J. H., Oh B. K., Choi J. W., Electrochem. Commun., 2010, 12(12), 1756—1759
[25]	Xu C. X., Su J. X., Xu X. H., Liu P. P., Zhao H. J., Tian F., Ding Y., J. Am. Chem. Soc., 2007, 129(1), 42—43
[26]	Liu R., Liu J. F., Zhou X. X., Sun M. T., Jiang G. B., Anal. Chem.,2011, 83(23), 9131—9137
[27]	Kafi A. K. M., Ahmadalinezhad A., Wang J. P., Thomas D. F., Chen A. C., Biosens-Bioelectron., 2010, 25(11), 2458—2463
[28]	Zhang G. J., Wang Y. N., Wang X., Chen Y., Zhou Y. M., Tang Y. W., Lu L. D., Bao J. C., Lu T. H., Appl. Catal. B: Environ., 2011, 102(3), 614—619
[29]	Szumełda T., Drelinkiewicz A., Lalik E., Kosydar R., Duraczyńska D., Gurgul J., Appl. Catal. B: Environ.,2018, 221, 393—405
[30]	Yuan T., Chen H. Y., Ma X. H., Feng J. J., Yuan P. X., Wang A. J., J. Colloid Interface Sci.,2018, 513, 324—330
[31]	Huang T., Moon S. K., Lee J. M., Sustainable Energy Fuels,2017, 1(3), 450—457
[32]	Sun D. D., Si L., Fu G. T., Liu C., Sun D. M., Chen Y., Tang Y. W., Lu T. H., J. Power Sources,2015, 280, 141—146
[33]	Wang Y. X., Xiong Z., Xia Y. Z., RSC Adv., 2017, 7(64), 40462—40469
[34]	Hu S. Z., Scudiero L., Ha S., Electrochem. Commun., 2014, 38, 107—109
[35]	Maiyalagan T., Wang X., Manthiram A., RSC Adv., 2014, 4(8), 4028—4033