基于第一性原理方法研究ReOx在ReOx-Rh/ZrO2和ReOx-Ir/ZrO2催化的甘油氢解反应中的作用机制

doi:10.1016/S1872-2067(12)60626-3

催化学报 ›› 2013, Vol. 34 ›› Issue (9): 1656-1666.DOI: 10.1016/S1872-2067(12)60626-3

基于第一性原理方法研究ReO_x在ReO_x-Rh/ZrO₂和ReO_x-Ir/ZrO₂催化的甘油氢解反应中的作用机制

关静^a, 陈秀芳^a, 彭功名^a, 王喜成^a, 曹泉^a, 兰峥岗^a,b, 牟新东^a

a 中国科学院青岛生物能源与过程研究所, 中国科学院生物基材料重点实验室, 山东青岛 266101;
b 中国科学院青岛生物能源与过程研究所, 青岛市太阳能与储能技术重点实验室, 山东青岛 266101

收稿日期:2013-04-20 修回日期:2013-05-20 出版日期:2013-09-16 发布日期:2013-08-28
通讯作者: 兰峥岗, 牟新东
基金资助:
山东省自然科学基金(ZR2010BQ001); 国家自然科学基金(21273260, 21201174, 21103213); 中国科学院百人计划; 中国科学院青岛生物能源与过程研究所所长创新基金.

Role of ReO_x in Re-modified Rh/ZrO₂ and Ir/ZrO₂ catalysts in glycerol hydrogenolysis：Insights from first-principles study

Jing Guan^a, Xiufang Chen^a, Gongming Peng^a, Xicheng Wang^a, Quan Cao^a, Zhenggang Lan^a,b, Xindong Mu^a

a Key Laboratory of Biobased Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, China;
b The Qingdao Key Lab of Solar Energy Utilization and Energy Storage Technology, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, Shandong, China

Received:2013-04-20 Revised:2013-05-20 Online:2013-09-16 Published:2013-08-28
Supported by:
This work was supported by the Natural Science Foundation of Shandong Province (ZR2010BQ001), the National Natural Science Foundation of China (21273260, 21201174 and 21103213), 100 Talents Program of the Chinese Academy of Sciences, and the Director Innovation Foundation of Chinese Academy of Sciences-Qingdao Institute of Bioenergy and Bioprocess Technology.

摘要/Abstract

摘要：

采用密度泛函理论研究了ZrO₂负载的Ru基、Rh基以及Re改性的Rh基、Ir基催化剂上甘油氢解生成1,2-丙二醇和1,3-丙二醇的热力学过程, 重点考察了ReO_x调变催化剂活性和选择性的作用机制. 结果表明, Ru/ZrO₂和Rh/ZrO₂催化剂上甘油分解经由脱水-加氢反应途径, 1,2-丙二醇的生成是热力学有利过程, 其中Ru基催化剂活性更高. 在Re修饰的Rh基和Ir基催化剂上, 反应遵循直接氢解机理, 其中金属表面解离的氢原子进攻ReO_x团簇上与醇盐紧邻的C-O键是催化甘油转化为丙二醇最核心的步骤. ReO_x-Rh/ZrO₂催化剂上1,2-丙二醇为主要产物, 并伴随1,3-丙二醇的生成, ReO_x的修饰则显著提高了Ir/ZrO₂催化剂上1,3-丙二醇选择性. 与单金属催化剂上发生的间接氢解机理相比, 修饰催化剂上1,3-丙二醇选择性的提高可主要归因于Rh(Ir)-Re协同催化的直接氢解反应过程, 其中羟基化铼官能团有利于末端醇盐中间体的生成. ReO_x-Ir/ZrO₂催化剂上较大的Ir-Re团簇使得末端金属醇盐的立体优选性比次级醇盐更为突出, 从而具有最高的1,3-丙二醇选择性.

关键词: 密度泛函理论, 甘油氢解, 丙二醇, 铼修饰, 金属催化剂, 热力学

Abstract:

The thermodynamics of glycerol hydrogenolysis to produce 1,2-propanediol (1,2-PDO) and 1,3-propanediol (1,3-PDO) over Ru/ZrO₂, Rh/ZrO₂, ReO_x-Rh/ZrO₂, and ReO_x-Ir/ZrO₂ were studied using density functional theory calculations, with a special focus on the mechanism controlling the activity and selectivity of the reactions. It is found that the decomposition of glycerol on Ru/ZrO₂ and Rh/ZrO₂ proceeds through a dehydration-hydrogenation mechanism. The formation of 1,2-PDO is thermodynamically favored, and the activity of the Ru-based catalyst is higher than that of the Rh-based one. In contrast, a direct hydrogenolysis mechanism is proposed for the Re-modified Rh and Ir catalysts, in which a dissociated H atom on the Rh(Ir) metal surface attacks the C-O bond neighboring the alkoxide species on the ReO_x cluster. In the presence of ReO_x-Rh/ZrO₂, the modified catalyst favors the production of 1,2-PDO, and 1,3-PDO production becomes competitive. However, the ReO_x-Ir/ZrO₂ catalyst significantly improves 1,3-PDO selectivity. The direct hydrogenolysis pathway, as opposed to the indirect hydrogenolysis mechanism for monometallic catalysts, may be the key to the high 1,3-PDO selectivity on the modified catalysts, where the hydroxylated Re group facilitates the formation of terminal alkoxide species rather than secondary alkoxides. Steric effects are important in preferential terminal alkoxide formation on the ReO_x-Ir/ZrO₂ catalysts because of the growth of large Ir-Re clusters, resulting in high selectivity for 1,3-PDO.

Key words: Density functional theory, Glycerol hydrogenolysis, Propanediol, Re-modified, Metal catalyst, Thermodynamics

关静, 陈秀芳, 彭功名, 王喜成, 曹泉, 兰峥岗, 牟新东. 基于第一性原理方法研究ReO_x在ReO_x-Rh/ZrO₂和ReO_x-Ir/ZrO₂催化的甘油氢解反应中的作用机制[J]. 催化学报, 2013, 34(9): 1656-1666.

Jing Guan, Xiufang Chen, Gongming Peng, Xicheng Wang, Quan Cao, Zhenggang Lan, Xindong Mu. Role of ReO_x in Re-modified Rh/ZrO₂ and Ir/ZrO₂ catalysts in glycerol hydrogenolysis：Insights from first-principles study[J]. Chinese Journal of Catalysis, 2013, 34(9): 1656-1666.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(12)60626-3

https://www.cjcatal.com/CN/Y2013/V34/I9/1656

参考文献

[1] Werpy T, Petersen G. Top Value Added Chemicals from Biomass. Volume I: Results of Screening for Potential Candidates from Sugars and Synthesis Gas. US DOE Report, 2004
[2] Nakagawa Y, Tomishige K. Catal Sci Technol, 2011, 1: 179
[3] Huang Z W, Cui F, Kang H X, Chen J, Zhang X Z, Xia C G. Chem Mater, 2008, 20: 5090
[4] Chaminand J, Djakovitch L, Gallezot P, Marion P, Pinel C, Rosier C. Green Chem, 2004, 6: 359
[5] Dasari M A, Kiatsimkul P P, Sutterlin W R, Suppes G J. Appl Catal A, 2005, 281: 225
[6] Werpy T A, Frye G Jr, Zacher A H, Miller D J. US Patent 6 841 085. 2005
[7] Perosa A, Tundo P. Ind Eng Chem Res, 2005, 44: 8535
[8] Lahr D G, Shanks B H. J Catal, 2005, 232: 386
[9] Miyazawa T, Kusunoki Y, Kunimori K, Tomishige K. J Catal, 2006, 240: 213
[10] Miyazawa T, Koso S, Kunimori K, Tomishige K. Appl Catal A, 2007, 329: 30
[11] Feng J, Fu H Y, Wang J B, Li R X, Chen H, Li X J. Catal Commun, 2008, 9: 1458
[12] Kurosaka T, Maruyama H, Naribayashi I, Sasaki Y. Catal Commun, 2008, 9: 1360
[13] Maris E P, Ketchie W C, Murayama M, Davis R J. J Catal, 2007, 251: 281
[14] Ma L, Li Y M, He D H. Chin J Catal (马兰, 李宇明, 贺德华. 催化学报), 2011, 32: 872
[15] Liu L J, Zhang Y H, Wang A Q, Zhang T. Chin J Catal (刘龙杰, 张艳华, 王爱琴, 张涛. 催化学报), 2012, 33: 1257
[16] Shimao A, Koso S, Ueda N, Shinmi Y, Furikado I, Tomishige K. Chem Lett, 2009, 38: 540
[17] Shinmi Y, Koso S, Kubota T, Nakagawa Y, Tomishige K. Appl Catal B, 2010, 94: 318
[18] Nakagawa Y, Shinmi Y, Koso S, Tomishige K. J Catal, 2010, 272: 191
[19] Deniel O M, DeLaRiva A, Kunkes E L, Datye A K, Dumesic J A, Davis R J. ChemCatChem, 2010, 2: 1107
[20] Montassier C, Giraud D, Barbier J. Stud Surf Sci Catal, 1988, 41: 165
[21] Montassier C, Menezo J C, Hoang L C, Renaud C, Barbier J. J Mol Catal, 1991, 70: 99
[22] Nimlos M R, Blanksby S J, Qian X H, Himmel M E, Johnson D K. J Phys Chem A, 2006, 110: 6145
[23] Auneau F, Michel C, Delbecq F, Pinel C, Sautet P. Chem Eur J, 2011, 17: 14288
[24] Coll D, Delbecq F, Aray Y, Sautet P. Phys Chem Chem Phys, 2011, 13: 1448
[25] Chia M, Pagan-Torres Y J, Hibbitts D, Tan Q H, Pham H N, Datye A K, Neurock M, Davis R J, Dumesic. J A. J Am Chem Soc, 2011, 133: 12675
[26] Guan J, Wang X C, Wang X Y, Mu X D. Sci China Chem, 2013, 56: 763
[27] Kresse G, Joubert D. Phys Rev B, 1999, 59: 1758
[28] Kresse G, Furthmueller J. Phys Rev B, 1996, 54: 11169
[29] Kresse G, Hafner J. Phys Rev B, 1994, 49: 14251
[30] Blöchl P E. Phys Rev B, 1994, 50: 17953
[31] Perdew J P, Wang Y. Phys Rev B, 1992, 45: 13244
[32] Monkhorst H J, Pack J D. Phys Rev B, 1976, 13: 5188
[33] Grau-Crespo R, Hernández N C, Sanz J F, DeLeeuw N H. J Phys Chem C, 2007, 111: 10448
[34] Yang Z X, Xie L G, Ma D W, Wang G T. J Phys Chem C, 2011, 115: 6730
[35] Pan Y X, Liu C J, Ge Q F. J Catal, 2010, 272: 227
[36] Li H J, Ho J J. J Phys Chem C, 2009, 113: 20139
[37] Chen H L, Peng W T, Ho J J, Hsieh H M. Chem Phys, 2008, 348: 161
[38] Olsen R A, Kroes G J, Baerends E J. J Chem Phys, 1999, 111: 11155
[39] German E D, Efremenko I, Sheintuch M. J Phys Chem A, 2001, 105: 11312
[40] Choi Y M, Liu P. J Am Chem Soc, 2009, 131: 13054
[41] Shetty S, van Santen R A, Stevens P A, Raman S. J Mol Catal A, 2010, 330: 73
[42] Zhou J X, Zhang J, Guo X W, Mao J B, Zhang S G. Green Chem, 2012, 14: 156
[43] Wang J H, Lee C S, Lin M C. J Phys Chem C, 2009, 113: 6681
[44] Nakagawa Y, Uehara K, Mizuno N. Inorg Chem, 2005, 44: 14
[45] Day V W, Klemperer W G, Schwartz C. J Am Chem Soc, 1987, 109: 6030

基于第一性原理方法研究ReO_x在ReO_x-Rh/ZrO₂和ReO_x-Ir/ZrO₂催化的甘油氢解反应中的作用机制

Role of ReO_x in Re-modified Rh/ZrO₂ and Ir/ZrO₂ catalysts in glycerol hydrogenolysis：Insights from first-principles study

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[2]	程璐, 陈许宁, 胡培君, 曹宵鸣. 双氧水对于单核铜分子筛催化甲烷直接氧化制甲醇反应性能的利弊[J]. 催化学报, 2023, 51(8): 135-144.
[3]	刘赵春, 宗雪, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. 金属掺杂SnO₂电化学还原CO₂制甲酸的计算研究[J]. 催化学报, 2023, 50(7): 249-259.
[4]	耿仕鹏, 陈利明, 陈海鑫, 王毅, 丁朝斌, 蔡丹丹, 宋树芹. 揭示层状晶态CoMoO₄的水裂解电催化机制: 从晶面选择到活性位点设计的理论研究[J]. 催化学报, 2023, 50(7): 334-342.
[5]	黄正清, 贺姝玥, 班涛, 高新, 许云华, 常春然. Pt-Cu合金催化剂上甲烷无氧偶联的机理与微观动力学研究: 从单原子位点到单团簇位点[J]. 催化学报, 2023, 48(5): 90-100.
[6]	井会娟, 龙军, 李欢, 傅笑言, 肖建平. 电催化硝酸盐还原合成氨电势相关性的计算见解[J]. 催化学报, 2023, 48(5): 205-213.
[7]	赵志月, 蒋志伟, 黄一哲, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, 罗惠霞, 严凯. 富空穴CoSi合金无溶剂无碱醇氧化[J]. 催化学报, 2023, 48(5): 175-184.
[8]	Sue-Faye Ng, 陈星竹, Joel Jie Foo, 熊墨, Wee-Jun Ong. 2D氮化碳: 通过调节非金属硼掺杂C₃N₅阐明宽酸性及碱性pH范围的光催化析氢的反应机理[J]. 催化学报, 2023, 47(4): 150-160.
[9]	陈成成, 刘芳庭, 张巧钰, 张正国, 刘琼, 方晓明. 理论设计和实验研究吡啶掺杂聚合氮化碳提升光催化CO₂还原性能[J]. 催化学报, 2023, 46(3): 91-102.
[10]	黄志鹏, 杨阳, 穆骏驹, 李根恒, 韩建宇, 任濮宁, 张健, 罗能超, 韩克利, 王峰. 利用金属-自由基相互作用调控自由基的定向转化[J]. 催化学报, 2023, 45(2): 120-131.
[11]	孟翔宇, 李睿, 杨峻懿, 许世明, 张辰晨, 尤可嘉, 马宝春, 管红霞, 丁勇. 六核环状钴配合物用于光催化CO₂到CO转化[J]. 催化学报, 2022, 43(9): 2414-2424.
[12]	商禹, 丁云轩, 张培立, 王梅, 贾玉飞, 徐云龙, 李亚晴, 范科, 孙立成. 吡啶氮或吡咯氮: 氮掺杂碳催化剂在电催化还原CO₂中活性中心研究[J]. 催化学报, 2022, 43(9): 2405-2413.
[13]	李楠, 王传义, 章柯, 吕海钦, 苑明哲, Detlef W. Bahnemann. 光催化转化低浓度NO的进展与展望[J]. 催化学报, 2022, 43(9): 2363-2387.
[14]	蒋婷婷, 谢伟伟, 耿仕鹏, 李如春, 宋树芹, 王毅. 构建氧空位调控的钼酸钴纳米片用于高效催化析氧反应[J]. 催化学报, 2022, 43(9): 2434-2442.
[15]	欧阳, 李松达, 王飞, 段心怡, 袁文涛, 杨杭生, 张泽, 王勇. 二氧化钛负载的铂纳米颗粒在CO和O₂环境下表面平台位点和台阶位点的可逆转变[J]. 催化学报, 2022, 43(8): 2026-2033.