Chinese Journal of Magnetic Resonance >
Analysis of Local Structure, Acidic Property and Activity of Solid Acids by Solid-State Nuclear Magnetic Resonance Spectroscopy
Received date: 2021-04-28
Online published: 2021-06-16
Supported by
Australian Research Council Discovery Projects(DP150103842);Australian Research Council Discovery Projects(DP180104010)
Solid acid is one of the most widely applied heterogeneous catalysts for industrial hydrocarbon conversion and biomass refining. It is crucial to understand the nature of solid acid such as its local structure and acidic properties. Such knowledge renders effective design of solid acid with better activity and stability for the desired reaction. Recently, solid-state nuclear magnetic resonance (SSNMR) spectroscopy has been applied as a powerful standard method for characterizing the local structure and acidic nature of solid acid in both qualitative and quantitative manners. Additionally, the applications of advanced two-dimensional SSNMR methodologies further reveal the symmetry of surface sites, spatial relationship of different sites, and thereby unmasking the structure-activity relationship. In this review, we summarize the general methods and SSNMR techniques for the routine characterization, focusing on the progresses in the understanding of local structure and acidic properties of solid acids via the application of SSNMR with or without probe molecules.
Wen-jie YANG , Jun HUANG . Analysis of Local Structure, Acidic Property and Activity of Solid Acids by Solid-State Nuclear Magnetic Resonance Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2021 , 38(4) : 460 -473 . DOI: 10.11938/cjmr20212913
| 1 | TANABE K. Solid acids and bases: their catalytic properties[M]. Elsevier, 2012. |
| 2 | HUANG J , JIANG Y , MARTHALA V R , et al. Regioselective H/D exchange at the Side-Chain of ethylbenzene on dealuminated zeolite H-Y studied by in situ MAS NMR-UV/Vis spectroscopy[J]. Chem Phys Chem, 2008, 9 (8): 1107- 1109. |
| 3 | YU Z , LI S , WANG Q , et al. Br?nsted/lewis acid synergy in H-ZSM-5 and H-MOR zeolites studied by 1H and 27Al DQ-MAS solid-state NMR spectroscopy[J]. J Phys Chem C, 2011, 115 (45): 22320- 22327. |
| 4 | ASTRUC D. Heterogeneous catalysis[M]. Organomet Chem Catal, 2007, 457-486. |
| 5 | GORTE R J , CROSSLEY S P . A perspective on catalysis in solid acids[J]. J Catal, 2019, 375, 524- 530. |
| 6 | WANG R D , XU B B , SONG Y H , et al. Methanol-water interaction in photocatalytic methanol reforming─An operando NMR study[J]. Chinese J Magn Reson, 2021, 38 (1): 43- 57. |
| 6 | 王睿迪, 徐贝贝, 宋艳红, 等. 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. |
| 7 | WU X Q , XU S T , ZHANG W N , et al. Direct mechanism of the first carbon-carbon bond formation in the methanol-to-hydrocarbons process[J]. Angew Chem Int Ed, 2017, 129 (31): 9167- 9171. |
| 8 | YE M , YANG Y N , ZHANG R , et al. Effects of co-catalysts and wavelength of light on the products of photocatalytic methanol reforming: An operando NMR study[J]. Chinese J Magn Reson, 2019, 36 (4): 490- 501. |
| 8 | 叶曼, 杨以宁, 张燃, 等. 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. |
| 9 | CHEN Y X , GONG K , JIAO F , et al. C-C bond formation in syngas conversion over zinc sites grafted on ZSM-5 Zeolite[J]. Angew Chem Int Ed, 2020, 59 (16): 6529- 6534. |
| 10 | 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. |
| 11 | WANG J X , FENG J W , CHEN J F , et al. Design and fabrication of a magic-angle spinning rotor for solid-state nuclear magnetic resonance probe[J]. Chinese J Magn Reson, 2019, 36 (4): 446- 455. |
| 11 | 王佳鑫, 冯继文, 陈俊飞, 等. 魔角旋转固体核磁共振探头中转子的研制[J]. 波谱学杂志, 2019, 36 (4): 446- 455. |
| 12 | KEELER J. Understanding NMR spectroscopy[M]. John Wiley & Sons, 2011. |
| 13 | LOWE I . Free induction decays of rotating solids[J]. Phys Rev Lett, 1959, 2 (7): 285. |
| 14 | HUNGER M. Solid-state NMR spectroscopy[M].//(CHESTER A W, DEROUANE E G, Eds.), Zeolite Characterization and Catalysis: A Tutorial, Springer Netherlands: Dordrecht, 2009, 65-105. |
| 15 | LIANG L X , DENG F , HOU G J . Quantitative cross polarization magic-angle spinning NMR spectroscopy in solids[J]. Chinese J Magn Reson, 2020, 37 (1): 1- 15. |
| 15 | 梁力鑫, 邓风, 侯广进. 固体核磁共振魔角旋转条件下的定量交叉极化技术(英文)[J]. 波谱学杂志, 2020, 37 (1): 1- 15. |
| 16 | HOU G J , DING S W , ZHANG L M , et al. Breaking the T1 constraint for quantitative measurement in magic angle spinning solid-state NMR spectroscopy[J]. J Am Chem Soc, 2010, 132 (16): 5538- 5539. |
| 17 | LI S H , ZHENG A M , SU Y C , et al. Extra-framework aluminium species in hydrated faujasite zeolite as investigated by two-dimensional solid-state NMR spectroscopy and theoretical calculations[J]. Phys Chem Chem Phys, 2010, 12 (15): 3895- 3903. |
| 18 | LUAN Z H , CHENG C F , HE H Y , et al. Thermal stability of structural aluminum in the mesoporous molecular sieve MCM-41[J]. J Phys Chem, 1995, 99 (26): 10590- 10593. |
| 19 | KENNEDY G J , AFEWORKI M , CALABRO D C , et al. 1H MAS NMR (magic-angle spinning nuclear magnetic resonance) techniques for the quantitative determination of hydrogen types in solid catalysts and supports[J]. Appl Spectrosc, 2004, 58 (6): 698- 704. |
| 20 | WANG Z C , JIANG Y J , JIN F Z , et al. Strongly enhanced acidity and activity of amorphous silica-alumina by formation of pentacoordinated AlV species[J]. J Catal, 2019, 372, 1- 7. |
| 21 | WANG Z C , LI T , JIANG Y J , et al. Acidity enhancement through synergy of penta-and tetra-coordinated aluminum species in amorphous silica networks[J]. Nat Commun, 2020, 11, 225. |
| 22 | ZHENG A, DENG F, LIU S. Acidity characterization of solid acid catalysts by solid-state 31P NMR of adsorbed phosphorus-containing probe molecules[M].//WEBB G A. Annu Rep NMR Spectrosc. APNMR, Academic Press. 2014, 47-108. |
| 23 | LI S H , LAFON O , WANG W Y , et al. Recent advances of solid-state NMR spectroscopy for microporous materials[J]. Adv Mater, 2020, 32 (44): 2002879. |
| 24 | LI S H , ZHOU L , ZHENG A M , et al. Recent advances in solid state NMR characterization of zeolites[J]. Chinese J Catal, 2015, 36 (6): 789- 796. |
| 25 | GABRIENKO A A , DANILOVA I G , ARZUMANOV S S , et al. Strong acidity of silanol groups of zeolite beta: Evidence from the studies by IR spectroscopy of adsorbed CO and 1H MAS NMR[J]. Microporous Mesoporous Mater, 2010, 131 (1-3): 210- 216. |
| 26 | BORONAT M , CORMA A . Factors controlling the acidity of zeolites[J]. Catal Lett, 2015, 145 (1): 162- 172. |
| 27 | PAZE C , ZECCHINA A , SPERA S , et al. Comparative IR and 1H-MAS NMR study of adsorption of CD3CN on zeolite H-β: evidence of the presence of two families of bridged Bronsted sites[J]. Phys Chem Chem Phys, 1999, 1 (10): 2627- 2629. |
| 28 | BORONAT M , CORMA A . Factors controlling the acidity of zeolites[J]. Catal Lett, 2015, 145 (1): 162- 172. |
| 29 | BARAN R , MILLOT Y , ONFROY T , et al. Influence of the nitric acid treatment on Al removal, framework composition and acidity of BEA zeolite investigated by XRD, FTIR and NMR[J]. Microporous Mesoporous Mater, 2012, 163, 122- 130. |
| 30 | GAO X Z , ZHANG Y , WANG X M , et al. Structure and Acidity changes in ultra-stable Y zeolites during hydrothermal aging: A solid-state NMR spectroscopy study[J]. Chinese J Magn Reson, 2020, 37 (1): 95- 103. |
| 30 | 高秀枝, 张翊, 王秀梅, 等. NMR研究超稳Y分子筛水热老化过程中结构与酸性的变化[J]. 波谱学杂志, 2020, 37 (1): 95- 103. |
| 31 | GABRIENKO A , DANILOVA I G , ARZUMANOV S S , et al. Direct measurement of zeolite Br?nsted acidity by FTIR spectroscopy: Solid-state 1H MAS NMR approach for reliable determination of the integrated molar absorption coefficients[J]. J Phys Chem C, 2018, 122 (44): 25386- 25395. |
| 32 | CHEN K Z , ABDOLRHAMANI M , SHEETS E , et al. Direct detection of multiple acidic proton sites in zeolite HZSM-5[J]. J Am Chem Soc, 2017, 139 (51): 18698- 18704. |
| 33 | ABDOLRAHMANI M , CHEN K , WHITE J . Assessment, control, and impact of br?nsted acid site heterogeneity in zeolite HZSM-5[J]. J Phys Chem C, 2018, 122 (27): 15520- 15528. |
| 34 | XU J, WANG Q, LI S H, et al. Solid-state NMR characterization of acid properties of zeolites and solid acid catalysts[M].//Solid-state NMR in zeolite catalysis. Springer, 2019, 159-197. |
| 35 | HAIJJAR R , MILLOT Y , MAN P P , et al. Two kinds of framework Al sites studied in BEA zeolite by X-ray diffraction, Fourier transform infrared spectroscopy, NMR techniques, and V probe[J]. J Phys Chem C, 2008, 112 (51): 20167- 20175. |
| 36 | ESCRIBANO V S , GARBARINO G , FINOCCHIO E , et al. γ-Alumina and amorphous silica-alumina: structural features, acid sites and the role of adsorbed water[J]. TOP CATAL, 2017, 60 (19, 20): 1554- 1564. |
| 37 | CREPEAU G , MONTOUILLOUT V , VIMONT A , et al. Nature, structure and strength of the acidic sites of amorphous silica alumina: an IR and NMR study[J]. J Phys Chem B, 2006, 110 (31): 15172- 15185. |
| 38 | BRUNNER E . Characterization of solid acids by spectroscopy[J]. Catal Today, 1997, 38 (3): 361- 376. |
| 39 | DEC S F , HERRING A M . Solid-state 1H NMR study of structures and dynamics of proton sites in group Ⅱ salts of 12-tungstophosphoric acid and related compounds[J]. J Phys Chem C, 2018, 122 (27): 15539- 15557. |
| 40 | HUANG J , JIANG Y J , REDDG MARTHALA V A , et al. In situ 1H MAS NMR investigations of the H/D exchange of alkylaromatic hydrocarbons on zeolites HY, La, Na-Y, and H-ZSM-5[J]. Microporous Mesoporous Mater, 2007, 99 (1, 2): 86- 90. |
| 41 | RIEMER T , SPIELBAUER D , HUNGER M , et al. Superacid properties of sulfated zirconia as measured by Raman and 1H MAS NMR spectroscopy[J]. J Chem Soc Chem Comm, 1994, 10, 1181- 1182. |
| 42 | GUN'KO V M , ZARKO V V , TUROV V V , et al. Characterization of fumed alumina/silica/titania in the gas phase and in aqueous suspension[J]. J Colloid Interface Sci, 1999, 220 (2): 302- 323. |
| 43 | BORGES L D , DE MACEDO J . Solid-state dealumination of zeolite Y: Structural characterization and acidity analysis by calorimetric measurements[J]. Microporous Mesoporous Mater, 2016, 236, 85- 93. |
| 44 | JIANG Y J , HUANG J , DAI W L , et al. Solid-state nuclear magnetic resonance investigations of the nature, property, and activity of acid sites on solid catalysts[J]. Solid State Nucl Magn Reson, 2011, 39 (3-4): 116- 141. |
| 45 | WANG Z C , JIANG Y J , LAFON O , et al. Br?nsted acid sites based on penta-coordinated aluminum species[J]. Nat Commun, 2016, 7, 13820. |
| 46 | LI S H , LI J , ZHENG A M , et al. Solid-state NMR characterization of the structure and catalytic reaction mechanism of solid acid catalysts[J]. ACTA PHYS-CHIM SIN, 2017, 33 (2): 270- 282. |
| 47 | YANG W J , WANG Z C , HUANG J , et al. Qualitative and quantitative analysis of acid properties for solid acids by solid-state nuclear magnetic resonance spectroscopy[J]. J Phys Chem C, 2021, 125 (19): 10179- 10197. |
| 48 | SONG C H , CHU Y Y , WANG M , et al. Cooperativity of adjacent Br?nsted acid sites in MFI zeolite channel leads to enhanced polarization and cracking of alkanes[J]. J Catal, 2017, 349, 163- 174. |
| 49 | PERRAS F A , WANG Z C , KOBAYASHI T , et al. Shedding light on the atomic-scale structure of amorphous silica-alumina and its Br?nsted acid sites[J]. Phys Chem Chem Phys, 2019, 21 (35): 19529- 19537. |
| 50 | GAO P , WANG Q , XU J , et al. Br?nsted/Lewis acid synergy in methanol-to-aromatics conversion on Ga-modified ZSM-5 zeolites, as studied by solid-state NMR spectroscopy[J]. ACS Catal, 2018, 8 (1): 69- 74. |
| 51 | PENG L M , GREY C P . Diphosphine probe molecules and solid-state NMR investigations of proximity between acidic sites in zeolite HY[J]. Microporous Mesoporous Mater, 2008, 116 (1-3): 277- 283. |
| 52 | CHEN K Z , HORSTMEIER S , NGUYEN V T , et al. Structure and catalytic characterization of a second framework Al(IV) site in zeolite catalysts revealed by NMR at 35.2 T[J]. J Am Chem Soc, 2020, 142 (16): 7514- 7523. |
| 53 | PENG L M , LIU Y , KIM N . Detection of Br?nsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques[J]. Nat Mater, 2005, 4 (3): 216- 219. |
| 54 | PENG L M , HUO H , GAN Z H . 17O MQMAS NMR studies of zeolite HY[J]. Microporous Mesoporous Mater, 2008, 109 (1-3): 156- 162. |
| 55 | PENG L M , HUO H , LIU Y , et al. 17O magic angle spinning NMR studies of Br?nsted acid sites in zeolites HY and HZSM-5[J]. J Am Chem Soc, 2007, 129 (2): 335- 346. |
| 56 | SHEN L , PENG L M . 17O solid-state NMR studies of oxygen-containing catalysts[J]. Chinese J Catal, 2015, 36 (9): 1494- 1504. |
| 57 | SHEN L , WU X P , WANG Y , et al. 17O solid-state NMR studies of ZrO2 nanoparticles[J]. J Phys Chem C, 2019, 12 (7): 4158- 4167. |
| 58 | SHEN L , WANG Y , DU J H , et al. Interactions of γ-alumina with water via multinuclear solid-state NMR spectroscopy[J]. Chem Cat Chem, 2020, 12 (6): 1569- 1574. |
| 59 | SUN T T , XU S T , XIAO D , et al. Water-induced structural dynamic process in molecular sieves under mild hydrothermal conditions: Ship-in-a-bottle strategy for acidity identification and catalyst modification[J]. Angew Chem Int Ed, 2020, 132 (46): 20853- 20862. |
| 60 | GUNTHER W R , MICHAELIS V K , CAPORINI M A , et al. Dynamic nuclear polarization NMR enables the analysis of Sn-Beta zeolite prepared with natural abundance 119Sn precursors[J]. J Am Chem Soc, 2014, 136 (17): 6219- 6222. |
| 61 | ZHENG A M , LIU S B , DENG F . 31P NMR chemical shifts of phosphorus probes as reliable and practical acidity scales for solid and liquid catalysts[J]. Chem Rev, 2017, 117 (19): 12475- 12531. |
| 62 | WANG Y X , XIN S H , CHU Y Y , et al. Influence of trimethylphosphine oxide loading on the measurement of zeolite acidity by solid-state NMR spectroscopy[J]. J Phys Chem C, 2021, 125 (17): 9497- 9506. |
| 63 | XU J , DENG F . Solid-state NMR in interdisciplinary research[J]. Acta Phys Chim Sin, 2020, 36 (4): 1912074- 0. |
| 63 | 徐君, 邓风. 多学科交叉研究中的固体核磁共振[J]. 物理化学学报, 2020, 36 (4): 1912074- 0. |
| 64 | ZHENG A M , HUANG S J , LIU S B , et al. Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules[J]. Phys Chem Chem Phys, 2011, 13 (33): 14889- 14901. |
| 65 | ZHENG A M , ZHANG H L , LU X , et al. Theoretical predictions of 31P NMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts[J]. J Phys Chem B, 2008, 112 (15): 4496- 4505. |
| 66 | HUANG J , JIANG Y J , REDDY MARTHALA V R , et al. Concentration and acid strength of hydroxyl groups in zeolites La, Na-X and La, Na-Y with different lanthanum exchange degrees studied by solid-state NMR spectroscopy[J]. Microporous Mesoporous Mater, 2007, 104 (1-3): 129- 136. |
| 67 | GONG K , LIU Z M , LIANG L X , et al. Acidity and local confinement effect in mordenite probed by solid-state NMR spectroscopy[J]. J Phys Chem Lett, 2021, 12 (9): 2413- 2422. |
| 68 | LUO Q , DENG F , YUAN Z Y , et al. Using trimethylphosphine as a probe molecule to study the acid sites in Al-MCM-41 materials by solid-state NMR spectroscopy[J]. J Phys Chem B, 2003, 107 (11): 2435- 2442. |
| 69 | ENGELHARDT G. Solid state NMR spectroscopy applied to zeolites[M].//Studies in surface science and catalysis, Elsevier: 2001, 137, 387-418. |
| 70 | HUANG J , JIANG Y J , REDDY MARTHALA V R , et al. Characterization and acidic properties of aluminum-exchanged zeolites X and Y[J]. J Phys Chem B, 2008, 112 (10): 3811- 3818. |
| 71 | HAW J F , NICHOLAS J B , XU T , et al. Physical organic chemistry of solid acids: lessons from in situ NMR and theoretical chemistry[J]. Acc Chem Res, 1996, 29 (6): 259- 267. |
| 72 | SU X , XU S T , TIAN P , et al. Investigation of the strong Br?nsted acidity in a novel SAPO-type molecular sieve, DNL-6[J]. J Phys Chem C, 2015, 119 (5): 2589- 2596. |
| 73 | GUNTHER W R , MICHAELIS V K , GRIFFIN R C , et al. Interrogating the Lewis acidity of metal sites in beta zeolites with 15N pyridine adsorption coupled with MAS NMR spectroscopy[J]. J Phys Chem C, 2016, 120 (50): 28533- 28544. |
| 74 | CHU Y Y , YU Z W , ZHENG A M , et al. Acidic strengths of Br?nsted and Lewis acid sites in solid acids scaled by 31P NMR chemical shifts of adsorbed trimethylphosphine[J]. J Phys Chem C, 2011, 115 (15): 7660- 7667. |
| 75 | YI X F , DING L H , LI G C , et al. Insights into the reaction mechanism of propene H/D exchange over acidic zeolite catalysts from theoretical calculations[J]. Catal Sci Technol, 2016, 6 (16): 6328- 6338. |
| 76 | KUBOTA T , OSUGA R , YOKOI T , et al. Consideration of acid strength of a single oh group on zeolites by isotope exchange reaction with ethane at high temperatures[J]. TOP CATAL, 2017, 60 (19-20): 1496- 1505. |
| 77 | SOMMER J , HABERMACHER D , JOST R , et al. Activation of small alkanes on solid acids. An H/D exchange study by liquid and solid-state NMR: the activation energy and the inhibiting effect of carbon monoxide[J]. J Catal, 1999, 181 (2): 265- 270. |
| 78 | KAZANSKY V B . Adsorbed carbocations as transition states in heterogeneous acid catalyzed transformations of hydrocarbons[J]. Catal Today, 1999, 51 (3-4): 419- 434. |
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