固-液-气三相环境下非均相苯加氢反应的原位核磁共振研究

doi:10.11938/cjmr20202829

摘要/Abstract

摘要：

本文使用原位核磁共振（NMR）方法成功实现了对固-液-气三相环境下加氢反应的在线监测.在反应过程中，无需分离产物.以Pd纳米颗粒粉末及不同晶面形貌的Pd催化剂作为研究对象，我们研究了反应压强、反应时间，以及催化剂表面性质对加氢反应的影响.结果表明，压强和反应时间都可以影响加氢反应产物的产率，使用暴露不同晶面的Pd共催化剂时，苯加氢产物不同.该原位NMR方法为研究固-液-气三相催化环境下的加氢反应机理提供了可能.

关键词: 原位核磁共振, 苯的加氢反应, 晶体形貌, 液体核磁共振, 非均相

Abstract:

The reaction of heterogeneous benzene hydrogenation reaction in a real solid-liquid-gas environment was studied by operando nuclear magnetic resonance (NMR) spectroscopy. During the reaction process, the products need not be separated before the test. Different catalysts (Pd nanoparticles and Pd with different crystal morphology) were performed to investigate the effects of pressure, reaction time and catalyst surface properties on benzene hydrogenation reaction. It was found that the pressure and the reaction time can affect the productivity of hydrogenation reaction, and the products of benzene hydrogenation reaction are determined by the exposed crystal surface of Pd catalysts. This operando NMR method provides a good opportunity to study the mechanism of solid-liquid-gas heterogeneous hydrogenation reaction.

Key words: operando NMR, benzene hydrogenation reaction, crystal morphology, liquid NMR, heterogeneous

中图分类号:

O482.53

随松,高国梁,王雪璐,魏达秀,姚叶锋. 固-液-气三相环境下非均相苯加氢反应的原位核磁共振研究[J]. 波谱学杂志, 2021, 38(2): 194-203.

Song SUI,Guo-liang GAO,Xue-lu WANG,Da-xiu WEI,Ye-feng YAO. An Operando Nuclear Magnetic Resonance Study on Solid-Liquid-Gas Heterogeneous Benzene Hydrogenation Reaction[J]. Chinese Journal of Magnetic Resonance, 2021, 38(2): 194-203.

图/表 8

图1

图2

图3

图4

图5

图6

图7

图8

参考文献 35

1	PORWAL G , GUPTA S , SREEDHALA S , et al. Mechanistic insights into the pathways of phenol hydrogenation on Pd nanostructures[J]. ACS Sustainable Chem Eng, 2019, 7 (20): 17126- 17136. doi: 10.1021/acssuschemeng.9b03392
2	FOPPA L , DUPONT J . Benzene partial hydrogenation: advances and perspectives[J]. Chem Soc Rev, 2015, 44 (7): 1886- 1897. doi: 10.1039/C4CS00324A
3	SÁNCHEZ V M , COJULUN J A , SCHERLIS D A . Dissociation free energy profiles for water and methanol on TiO₂ surfaces[J]. Chem Soc Rev, 2010, 114 (26): 11522- 11526.
4	ZHANG W P , XU S T , HAN X W , et al. In situ solid-state NMR for heterogeneous catalysis: a joint experimental and theoretical approach[J]. Chem Soc Rev, 2012, 41 (1): 192- 210. doi: 10.1039/C1CS15009J
5	XU S T , ZHANG W P , LIU X C , et al. Enhanced in situ continuous-flow MAS NMR for reaction kinetics in the nanocages[J]. J Am Chem Soc, 2009, 131 (38): 13722- 13727. doi: 10.1021/ja904304h
6	TONG Y Y , WIEKOWSKI A , OLDFIELD E . NMR of electrocatalysts[J]. J Phys Chem B, 2002, 106 (10): 2434- 2446. doi: 10.1021/jp0129939
7	CHAN K W H , WIECKOWSKI A . Probing adsorbates on Pt electrode surfaces by the use of ¹³C spin-echo NMR studies of generated from methanol electrosorption[J]. J Eletronchem Soc, 1990, 137 (1): 367- 368. doi: 10.1149/1.2086433
8	CATTANEO A , VILLA D , ANGIONI S , et al. Operando electrochemical NMR microscopy of polymer fuel cells[J]. Energy Environ Sci, 2015, 8 (8): 2383- 2388. doi: 10.1039/C5EE01668A
9	BLANC F , LESKES M , GREW C P . In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells[J]. Acc Chem Res, 2013, 46 (9): 1952- 1963. doi: 10.1021/ar400022u
10	CHEM T , FENG Z , WU G , et al. Mechanistic studies of photocatalytic reaction of methanol for hydrogen production on Pt/TiO₂ by in situ Fourier transform IR and time-resolved IR spectroscopy[J]. J Phys Chem C, 2007, 111 (22): 8005- 8014. doi: 10.1021/jp071022b
11	LIU W Q , SONG Y H , WANG X L , et al. The mechanism study of photocatalytic methanol reforming by operando nuclear magnetic resonance spectroscopy[J]. Chinese J Magn Reson, 2019, 36 (3): 298- 308.
	刘文卿, 宋艳红, 王雪璐, 等. 光催化甲醇重整机理的原位核磁共振研究[J]. 波谱学杂志, 2019, 36 (3): 298- 308.
12	ROTH D C M , KINDERVATER P , RAICH H P , et al. Continuous ¹H and ¹³C signal enhancement in NMR spectroscopy and MRI using parahydrogen and hollow-fiber membranes[J]. Angew Chem, 2010, 122 (45): 8536- 8540. doi: 10.1002/ange.201002725
13	KLIEWER C J , BIERI M , SOMORJAI G A . Hydrogenation of the α, β-unsaturated aldehydes acrolein, crotonaldehyde, and prenal over Pt single crystals: a kinetic and sum-frequency generation vibrational spectroscopy study[J]. J Am Chem Soc, 2009, 131 (29): 9958- 9966. doi: 10.1021/ja8092532
14	TSUNG C K , KUHN J N , HUANG W , et al. Sub-10 nm platinum nanocrystals with size and shape control: catalytic study for ethylene and pyrrole hydrogenation[J]. J Am Chem Soc, 2009, 131 (16): 5816- 5822. doi: 10.1021/ja809936n
15	KLIEWER C J , ALIAGA C , BIERI M , et al. Furan hydrogenation over Pt (111) and Pt (100) single-crystal surfaces and Pt nanoparticles from 1 to 7 nm: a kinetic and sum frequency generation vibrational spectroscopy study[J]. J Am Chem Soc, 2010, 132 (37): 13088- 13095. doi: 10.1021/ja105800z
16	PUSHKAREW V V , MUSSELWHITE N , AN K , et al. High structure sensitivity of vapor-phase furfural decarbonylation/hydrogenation reaction network as a function of size and shape of Pt nanoparticles[J]. Nano Lett, 2012, 12 (10): 5196- 5201. doi: 10.1021/nl3023127
17	BRATLIE K M , LEE H , KOMVOPOULOS K , et al. Platinum nanoparticle shape effects on benzene hydrogenation selectivity[J]. Nano Lett, 2007, 7 (10): 3097- 3101. doi: 10.1021/nl0716000
18	NARAYANAN R , EI-SAYED M A . Catalysis with transition metal nanoparticles in colloidal solution: nanoparticle shape dependence and stability[J]. J Phys Chem B, 2005, 109 (26): 12663- 12676. doi: 10.1021/jp051066p
19	BERHAULT G , BISSON L , THOMAZEAU C , et al. Preparation of nanostructured Pd particles using a seeding synthesis approach-Application to the selective hydrogenation of buta-1, 3-diene[J]. Appl Catal A-Gen, 2007, 327 (1): 32- 43. doi: 10.1016/j.apcata.2007.04.028
20	CRESPO-QUESADA M , YARULIN A , JIN M S , et al. Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective?[J]. J Am Chem Soc, 2011, 133 (32): 12787- 12794. doi: 10.1021/ja204557m
21	KATANO S , KATO H S , KAWAI M , et al. Selective partial hydrogenation of 1, 3-butadiene to butene on Pd(110): ? specification of reactant adsorption states and product stability[J]. J Phys Chem B, 2003, 107 (16): 3671- 3674. doi: 10.1021/jp022410a
22	PRASAD K H V , PRASAD K B S , MALLIKARJUNAN M M , et al. Self-poisoning and rate multiplicity in hydrogenation of benzene[J]. J Catal, 1983, 84 (1): 65- 73. doi: 10.1016/0021-9517(83)90086-6
23	JENKINS G I , RIDEAL S . The catalytic hydrogenation of ethylene at a nickel surface. Part Ⅱ. The reaction mechanism[J]. J Chem Soc, 1955, 2496- 2500. doi: 10.1039/jr9550002496
24	JENKⅡNS G I , RIDEAL S . The catalytic hydrogenation of ethylene at a nickel surface. Part I. The chemisorption of ethylene[J]. J Chem Soc, 1955, 2490- 2496. doi: 10.1039/jr9550002490
25	ROONEY J J . The exchange with deuterium of two cycloalkanes on palladium films: π-Bonded intermediates in heterogeneous catalysis[J]. J Catal, 1963, 2 (1): 53- 57. doi: 10.1016/0021-9517(63)90138-6
26	LUO M H , LU P , YAO W F , et al. Shape and composition effects on photocatalytic hydrogen production for Pt-Pd Alloy cocatalysts[J]. ACS Appl Mater Interfaces, 2016, 8 (32): 20667- 20674. doi: 10.1021/acsami.6b04388
27	GOTTLIEB H E , KOTLYAR V , NUDELMAN A . NMR chemical shifts of common laboratory solvents as trace impurities[J]. J Org Chem, 1997, 62 (21): 7512- 7515. doi: 10.1021/jo971176v
28	FRASER R R , RENAUD R N . The steric effect in the platinum-catalyzed exchange reaction between aromatic ring protons and deuterium oxide[J]. J Am Chem Soc, 1966, 88 (19): 4365- 4370. doi: 10.1021/ja00971a011
29	ZHAO E W , MALIGAL-GANESH R , DU Y , et al. Surface-mediated hyperpolarization of liquid water from parahydrogen[J]. Chem, 2018, 4 (6): 1387- 1403. doi: 10.1016/j.chempr.2018.03.004
30	NELSON N C , MANZANO J S N , SADOW A D , et al. Selective hydrogenation of phenol catalyzed by palladium on high-surface-area ceria at room temperature and ambient pressure[J]. ASC Catal, 2015, 5 (4): 2051- 2061.
31	VITOS L , RUBAN A , SKRIVER H L , et al. The surface energy of metals[J]. Surf Sci, 1998, 411 (1/2): 186- 202.
32	LIN C J , HUANG S H , LAI N C , et al. Efficient room-temperature aqueous-phase hydrogenation of phenol to cyclohexanone catalyzed by Pd nanoparticles supported on mesoporous MMT-1 silica with unevenly distributed functionalities[J]. ACS Catal, 2015, 5 (7): 4121- 4129. doi: 10.1021/acscatal.5b00380
33	WANG Y , YAO J , LI H R , et al. Highly selective hydrogenation of phenol and derivatives over a Pd@carbon nitride catalyst in aqueous media[J]. J Am Chem Soc, 2011, 133 (8): 2362- 2365. doi: 10.1021/ja109856y
34	ZHOU H , HAN B B , LIU T Z , et al. Selective phenol hydrogenation to cyclohexanone over alkali-metal-promoted Pd/TiO₂ in aqueous media[J]. Green Chem, 2017, 19 (15): 3585- 3594. doi: 10.1039/C7GC01318C
35	LI G F , HAN J Y , WANG H , et al. Role of dissociation of phenol in its selective hydrogenation on Pt (111) and Pd (111)[J]. ACS Catal, 2015, 5 (3): 2009- 2016. doi: 10.1021/cs501805y

[1]	张书怀,马慧,郭朝晖,马敏珺,乔岩,王英雄. 正丁醇/丙酸与腐殖酸相互作用的NMR研究[J]. 波谱学杂志, 2021, 38(3): 301-312.
[2]	窦梦雨,赵奇,侯相林,刘雷,唐明兴,王英雄. 蒽加氢产物的结构指认和定量核磁共振分析[J]. 波谱学杂志, 2021, 38(2): 239-248.
[3]	李玉江, 赵伟, 郭晓河, 陶乐, 张祥, 张海艳, 赵天增. 盐酸马尼地平的核磁共振数据解析[J]. 波谱学杂志, 2021, 38(1): 110-117.
[4]	王睿迪, 徐贝贝, 宋艳红, 王雪璐, 姚叶锋. 原位核磁共振技术研究光催化甲醇重整过程中甲醇与水的相互作用[J]. 波谱学杂志, 2021, 38(1): 43-57.
[5]	黄珊珊, 姚叶锋, 李鹏, 何培忠. 液体核磁共振 HSQC 实验的量子化学计算与模拟[J]. 波谱学杂志, 2021, 38(1): 32-42.
[6]	周中高, 谢倩, 元洋洋, 李静, 路东亮, 陈正旺. 吡喃葡糖基氮杂环卡宾-钯(II)-吡啶配合物的NMR研究[J]. 波谱学杂志, 2020, 37(4): 505-514.
[7]	杨以宁, 王雪璐, 姚叶锋. 原位核磁共振技术研究反应环境对光催化甲醇重整过程的影响[J]. 波谱学杂志, 2020, 37(1): 104-113.
[8]	宁彩芳, 马敏珺, 郭朝晖, 张书怀, 乔岩, 王英雄. PAMAM树状大分子与5-氟尿嘧啶相互作用的NMR研究[J]. 波谱学杂志, 2019, 36(4): 555-562.
[9]	林晓晴, 李弘, 詹昊霖, 杜世佳, 黄玉清, 陈忠. 高分辨率核磁共振纯化学位移谱新方法及其应用[J]. 波谱学杂志, 2019, 36(4): 425-436.
[10]	叶曼, 杨以宁, 张燃, 王雪璐, 姚叶锋. 原位核磁共振技术研究共催化剂类型以及光照波长对甲醇光催化重整产物的影响[J]. 波谱学杂志, 2019, 36(4): 490-501.
[11]	刘文卿, 宋艳红, 王雪璐, 姚叶锋. 光催化甲醇重整机理的原位核磁共振研究[J]. 波谱学杂志, 2019, 36(3): 298-308.
[12]	万至彬, 宋建会, 郭鸣明. 原位液体核磁共振在高分子材料表征领域的应用[J]. 波谱学杂志, 2019, 36(3): 408-424.
[13]	俞刚金, 周志明, 吕明, 钱胜涛, 孔渝华, 张许, 毛诗珍, 刘买利. 煤基乙二醇中杂质1,2-丁二醇的NMR定性定量分析[J]. 波谱学杂志, 2019, 36(1): 55-64.
[14]	魏会强, 于江, 毕常芬, 宁洪鑫, 李祎亮, 刘强. N-异丁酰基-3'-O-(1-氟-1,1,3,3-四异丙基-1,3-二硅氧烷-3-基)-2'-苄氧羰基鸟苷的NMR研究[J]. 波谱学杂志, 2019, 36(1): 93-102.
[15]	李红卫, 袁志良, 夏斌. 扩散序谱(DOSY)实验测定缓冲体系中蛋白质表观分子量[J]. 波谱学杂志, 2018, 35(3): 280-286.