石墨烯负载Pt-Pd催化剂的制备、催化制氢性能及机理研究

doi:10.7503/cjcu20170720

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (5): 949.doi: 10.7503/cjcu20170720

石墨烯负载Pt-Pd催化剂的制备、催化制氢性能及机理研究

鲁礼林^1,², 舒红飞², 阮祝华², 倪嘉琪², 张海军¹

1. 武汉科技大学省部共建耐火材料与冶金国家重点实验室, 2. 化学与化工学院, 煤转化与新型炭材料湖北省重点实验室, 武汉 430081

收稿日期:2017-11-10 出版日期:2018-04-10 发布日期:2018-04-10
作者简介:
联系人简介: 鲁礼林, 男, 博士, 副教授, 主要从事能源催化方面的研究. E-mail: lulilin@wust.edu.cn
基金资助:
国家自然科学基金(批准号: 21671154, U1732147)、武汉科技大学省部共建耐火材料与冶金国家重点实验室青年基金(批准号: 2016QN06)和绿色制造与节能减排技术研究中心开放基金(批准号: B1206)资助.

Preparation of Graphene-supported Pt-Pd Catalyst and Its Catalytic Activity and Mechanism for Hydrogen Generation Reaction^†

LU Lilin^1,^2,^*, SHU Hongfei², RUAN Zhuhua², NI Jiaqi², ZHANG Haijun¹

1. State Key Laboratory of Refractories and Metallurgy, 2. School of Chemistry and Chemical Engineering, Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, Wuhan University of Science and Technology, Wuhan 430081, China

Received:2017-11-10 Online:2018-04-10 Published:2018-04-10
Contact: LU Lilin
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21671154, U1732147), the Youth Fund of State Key Laboratory of Refractories and Metallurgy, China(No.2016QN06) and the Open Fund of Research Center of Green Manufacturing and Energy-saving and Emission Reduction Technology, China(No.B1206).

摘要/Abstract

摘要：

以氧化石墨烯为载体, 采用乙醇共还原法制备了石墨烯负载Pt-Pd双金属纳米催化剂, 并将其用于催化碱性硼氢化钾(KBH₄)水解制氢研究. 采用X射线衍射(XRD)分析和透射电子显微镜(TEM)等手段表征了催化剂的微观形貌和结构, 发现当金属催化剂中Pt/Pd摩尔比为1∶1时, Pt-Pd双金属催化剂颗粒可均匀地负载于石墨烯载体表面, 而且粒径比单金属催化剂和其它组成的双金属催化剂粒径更小, 约为5.6 nm. 将该催化剂用于催化碱性条件下KBH₄水解制氢实验, 结果表明, 金属催化剂的化学组成对其催化性能有明显影响, 当Pt/Pd摩尔比为1∶1时其催化活性高于其它化学组成(Pt/Pd摩尔比为4∶1或1∶4)的Pt-Pd双金属催化剂, 催化活性可达4380 mo $l H 2$ ·mo $l M - 1$ ·h^-1, 比Pt单金属催化剂活性提高约52%, 为Pd单金属催化剂活性的4倍. 通过催化反应动力学研究发现, Pt-Pd双金属催化剂催化KBH₄水解制氢反应的活化能约为20.90 kJ/mol, 催化剂具有较佳的耐久性, 连续使用3次后催化效率仍可达首次催化反应效率的83%. 利用密度泛函理论研究了催化剂催化KBH₄水解反应的机制, 发现双金属纳米催化剂可以明显降低硼氢化物水解反应决速步骤基元反应的势垒, 从而显著提高催化剂的催化活性.

关键词: 催化制氢, Pt-Pd双金属催化剂, 硼氢化钾, 反应机理

Abstract:

The graphene-supported nano Pt-Pd bimetallic catalysts with various chemical compositions(Pt/Pd molar ratio: 4∶1, 1∶1, 1∶4) were prepared via simple ethanol reduction method by reflux of graphene oxide(GO) and metallic salts in ethanol/water solvent for 5.5 h at 88 ℃. For comparison, graphene-supported Pt, Pd monometallic catalysts were also synthesized under the same experimental conditions. The morphology of as-prepared catalysts was characterized by XRD and TEM, the results indicate that chemical composition of metallic catalysts shows distinct influence on the particle morphology and size, the Pt-Pd bimetallic catalyst particles disperse on the surface of graphene support most evenly with the average diameter of approximately 5.6 nm when the Pt/Pd molar ratio was set as 1∶1. Their catalytic activities for hydrolysis reaction of alkaline potassium borohydride(pH=12.0) were investigated, the catalytic experiment results demonstrate that the catalytic activities significantly depend on chemical composition of metallic catalyst, among them the Pt-Pd bimetallic catalyst with the molar ratio of 1∶1 displays higher activity than other Pt-Pd bimetallic catalysts(Pt/Pd molar ratios of 1∶4 and 4∶1) and Pt, Pd monometallic catalysts, the hydrogen generation efficiency of graphene-supported nano Pt-Pd(molar ratio 1∶1) bimetallic catalysts is about 4380 mo $l H 2$ ·mo $l M - 1$ ·h^-1, which is higher than graphene-supported Pt catalyst by 52% and approximately as four-fold as graphene-supported Pd catalyst. Investigation on the catalytic durability demonstrated that about 83% of the initial catalytic activity was retained even after three cycles. Catalytic reaction kinetics studies manifest the activation energy of borohydride hydrolysis reaction catalyzed by graphene supported Pt/Pd(molar ratio 1∶1) bimetallic catalyst is about 20.90 kJ/mol, which is distinctly lower than those of the reaction catalyzed by Pt/C and Ru/C catalysts. DFT calculations based on M55 model revealed that the barrier height of rate-determining step catalyzed by Pt25Pd30 are distinctly lower than that catalyzed by Pd55 and Pt55, indicating the graphene supported Pt-Pd(Pt/Pd molar ratio 1∶1) possess more excellent catalytic activity.

Key words: Catalytic hydrogen generation, Pt-Pd bimetallic catalyst, Potassium borohydride, Reaction mechanism

中图分类号:

O643

TrendMD:

鲁礼林, 舒红飞, 阮祝华, 倪嘉琪, 张海军. 石墨烯负载Pt-Pd催化剂的制备、催化制氢性能及机理研究. 高等学校化学学报, 2018, 39(5): 949.

LU Lilin,SHU Hongfei,RUAN Zhuhua,NI Jiaqi,ZHANG Haijun. Preparation of Graphene-supported Pt-Pd Catalyst and Its Catalytic Activity and Mechanism for Hydrogen Generation Reaction^†. Chem. J. Chinese Universities, 2018, 39(5): 949.

图/表 6

Fig.1 Catalytic activities of graphene-supported metallic catalysts for hydrolysis reaction of KBH4(A) and the durability of graphene-supported Pt-Pd[n(Pt)/n(Pd)=1∶1] bimetallic catalyst(B) Note:(A) Catalyst: a. Pt; b. n(Pt)/n(Pd)=4∶1; c. n(Pt)/n(Pd)=1∶1; d. n(Pt)/n(Pd)=1∶4; e. Pd.

Fig.2 Arrhenius plots for the reaction rate of hydrolysis of KBH4 catalyzed by graphene-supported Pt-Pd[n(Pt)/n(Pd)=1∶1] bimetallic catayst

Fig.3 XRD patterns of graphite(a), graphene oxide(b) and the as-prepared graphene-supported Pt-Pd[n(Pt)/n(Pd)=1∶1] bimetallic catayst(c)

Fig.4 TEM images of graphene(A,A'), graphene-supported Pd catalyst(B,B'), graphene-supported Pt-Pd catalysts with Pt/Pd molar ratios of 1∶4(C,C'), 1∶1(D,D'), 4∶1(E,E') and graphene-supported Pt catalyst(F, F') with different magnifications

Fig.5 Optimized geometries of absorption complexes of BH4- on Pt55(A), Pd55(B) and Pt25Pd30(C) with the corresponding absorption energies(kJ/mol)

Fig.6 BLYP/DNP calculated energetic profiles for the rate-determining step in the borohydride hydrolysis catalyzed by Pd55(Ⅰ), Pt55(Ⅱ) and Pt25Pd30(Ⅲ)

参考文献 28

[1]	Marrero-Alfonso E.Y., Beaird A. M., Davis T. A., Matthews M. A., Ind. Eng. Chem. Res., 2009, 48(8), 3703—3712
[2]	Liu J.X., Song Y. A., Huang Y. D., Chem. [J]. Chinese Universities, 2016, 37(7), 1372—1379
	(刘佳欣, 宋义安, 黄玉东. 高等学校化学学报, 2016, 37(7), 1372—1379)
[3]	Tian Y., Li Y.X., Peng S. Q., Chem. [J]. Chinese Universities, 2017, 38(10), 1841—1849
	(田毅, 李越湘, 彭绍琴. 高等学校化学学报, 2017, 38(10), 1841—1849)
[4]	Schlesinger H.I., Brown H. C., Finholt A. B., Gilbreath J. R., Hockstra H. R., Hydo E. K., [J]. Am. Chem. Soc., 1953, 75(1), 215—219
[5]	Gu R., Zhang M., Wang C.Y., Huang W. J., Liu D. M., Chem. [J]. Chinese Universities, 2016, 37(4), 688—692
	(顾润, 张明, 王春阳, 黄维军, 柳东明. 高等学校化学学报, 2016, 37(4), 688—692)
[6]	Yadav M., Xu Q., Energy Environ.Sci., 2012, 5(12), 9698—9725
[7]	Demirci U.B., Miele P., Energy Environ. Sci., 2009, 2(6), 627—637
[8]	Tu G.P., He J. L., Xiao X. Z., Chen L. X., Ren Q. J., Du X. Y., Luo M. E., Chem. [J]. Chinese Universities, 2016, 37(10), 1757—1762
	(屠国平, 何剑灵, 肖学章, 陈立新, 任钱江, 杜锡勇, 骆明儿. 高等学校化学学报, 2016, 37(10), 1757—1762)
[9]	Zhang Q., Mohring R.M., Ind. Eng. Chem. Res., 2009, 48(3), 1603—1607
[10]	Audrieux J., Demirci U.B., Hannauer J., Gervais C., Goutaudier C., Miele P., Int. [J]. Hydrogen Energ., 2011, 36(1), 224—233
[11]	Liu B.H., Li Z. P., [J]. Power Source, 2009, 187(2), 527—534
[12]	Li C., Peng P., Zhou D.W., Wan L., Int. [J]. Hydrogen Energ., 2011, 36(22), 14512—14526
[13]	Keceli E., Ozkar S., J. Mol. Catal. A: Chem., 2008, 286(1/2), 87—91
[14]	Lu L.L., Zhang H. J., Zhang S. W., Li F. L., Angew. Chem., Int. Ed., 2015, 54(32), 9328—9332
[15]	Amendola S.C., Sharp-Goldman S. L., Janjua M. S., Kelly M. T., Petillo P. J., Binder M., [J]. Power Source, 2000, 85(2), 186—189
[16]	Brown H.C., Brown C. A., [J]. Am. Chem. Soc., 1962, 84(8), 1493—1494
[17]	Patel N., Patton B., Zanchetta C., Fernandes R., Guella G., Kale A., Miotello A., Int. J.Hydrogen Energ., 2008, 33(1), 287—292
[18]	Hung T.F., Kuo H. C., Tsai C. W., Chen H. M., Liu R. S., Weng B. J., Lee J. F., [J]. Mater. Chem., 2011, 21(32), 11754—11759
[19]	Zhang H., Lu L., Kawashima K., Okumura M., Haruta M., Toshima N., Adv. Mater., 2015, 27(8), 1383—1388
[20]	Zhang H., Lu L., Cao Y., Du S., Cheng Z., Zhang S., Materials Research Bulletin, 2014, 49(1), 393—398
[21]	Liu C.H., Chen B. H., Hsueh C. L., Ku J. R., Jeng M. S., Tsau F., Int. [J]. Hydrogen Energ., 2009, 34(5), 2153—2163
[22]	Kong D.C., Gu Y. J., Xiang S., Wang P., Cheng J., Zhang H. J., Zhang S. W., Chem. J. Chinese Universities, 2013, 34(10), 2377—2382(孔德成, 古亚军, 向胜, 王鹏, 成君, 张海军, 张少伟. 高等学校化学学报, 2013, 34(10), 2377—2382)
[23]	Zhao W.G., Su L., Zhou Z. N., Zhang H. J., Lu L. L., Zhang S. W., Acta Phys. Chim. Sin., 2015, 31(1), 145—152
	(赵万国, 苏丽, 周振宁, 张海军, 鲁礼林, 张少伟. 物理化学学报, 2015, 31(1), 145—152)
[24]	Jiao C., Huang Z., Wang X., Zhang H., Lu L., Zhang S., RSC Adv., 2015, 5(43), 34364—34371
[25]	Li W., Zhao W., Zhou X., Su L., Zhang H., Lu L., Zhang S., Chem. J. Chinese Universities, 2014, 35(10), 2164—2169
	(李文绮, 赵万国, 周兴赟, 苏丽, 张海军, 鲁礼林, 张少伟. 高等学校化学学报, 2014, 35(10), 2164—2169)
[26]	Hummers W., Offeman R., [J]. Am. Chem. Soc., 1958, 80(6), 1339—1339
[27]	Guella G., Patton B., Miotello A., J. Phys. Chem. C, 2007, 111(50), 18744—18750
[28]	Shang Y., Chen R., Energy Fuels, 2006, 20(5), 2142—2148

石墨烯负载Pt-Pd催化剂的制备、催化制氢性能及机理研究

Preparation of Graphene-supported Pt-Pd Catalyst and Its Catalytic Activity and Mechanism for Hydrogen Generation Reaction^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价

[1]	周紫璇, 杨海艳, 孙予罕, 高鹏. 二氧化碳加氢制甲醇多相催化剂研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220235.
[2]	杨丹, 刘旭, 戴翼虎, 祝艳, 杨艳辉. 金团簇电催化二氧化碳还原反应的研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220198.
[3]	任娜娜, 薛洁, 王治钒, 姚晓霞, 王繁. 热力学数据对1, 3-丁二烯燃烧特性的影响[J]. 高等学校化学学报, 2022, 43(6): 20220151.
[4]	孙翠红, 吕立强, 刘迎, 王妍, 杨静, 张绍文. 硝酸异丙酯与Cl原子、 OH和NO₃自由基反应的机理及动力学[J]. 高等学校化学学报, 2022, 43(2): 20210591.
[5]	程媛媛, 郗碧莹. ·OH自由基引发CH₃SSC $H 3 •$ ⁺自由基裂解反应机理的理论研究[J]. 高等学校化学学报, 2022, 43(10): 20220271.
[6]	孟繁伟, 高琦, 叶青, 李晨曦. Cu-SAPO-18催化剂氨选择性催化还原NO_x钾中毒机理的研究[J]. 高等学校化学学报, 2021, 42(9): 2832.
[7]	杨一莹, 朱荣秀, 张冬菊, 刘成卜. 金催化炔基苯并二𫫇英环化合成8-羟基异香豆素的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2299.
[8]	李心怡, 刘永军. 人工设计逆醛缩酶RA95.5-8F催化β-羟基酮C—C裂解的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2306.
[9]	李宜蔚, 申屠江涛, 王静波, 李象远. 燃烧反应机理构建的极小反应网络方法： C1燃料燃烧[J]. 高等学校化学学报, 2021, 42(6): 1871.
[10]	田胜侨, 韦美菊. Rh(Ⅱ)催化吲哚衍生物[3+3]环化机理及产物性质分析[J]. 高等学校化学学报, 2021, 42(6): 1899.
[11]	任颖, 李昌华, 王涛, 薛珊珊, 张婷婷, 贾建峰, 武海顺. 钯催化氧化N—H键羰基化反应合成1,3,4⁃噁二唑⁃2(3H)⁃酮杂环化合物机理的理论研究[J]. 高等学校化学学报, 2021, 42(6): 1793.
[12]	桂晨, 王颢霖, 邵柏璇, 杨育景, 徐光青. 熔盐辅助法制备g-C₃N₄纳米结构及其光催化制氢性能[J]. 高等学校化学学报, 2021, 42(3): 827.
[13]	孙亚光, 张含烟, 明涛, 徐宝彤, 高雨, 丁茯, 徐振和. ZnIn₂S₄/g-C₃N₄复合材料的制备及可见光催化制氢性能[J]. 高等学校化学学报, 2021, 42(10): 3160.
[14]	齐国栋, 叶晓栋, 徐君, 邓风. 分子筛上糖类催化转化的核磁共振研究[J]. 高等学校化学学报, 2021, 42(1): 148.
[15]	毛庆,赵健,刘松,郭唱,李冰玉,徐可一,曹自强,黄延强. Ni单原子催化剂表面CO₂电还原动力学的电化学谱学解析[J]. 高等学校化学学报, 2020, 41(5): 1058.

石墨烯负载Pt-Pd催化剂的制备、催化制氢性能及机理研究

Preparation of Graphene-supported Pt-Pd Catalyst and Its Catalytic Activity and Mechanism for Hydrogen Generation Reaction†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价

Preparation of Graphene-supported Pt-Pd Catalyst and Its Catalytic Activity and Mechanism for Hydrogen Generation Reaction^†