Acidity and Basicity of Solid Acid Catalysts Studied by Solid-State NMR

doi:10.11938/cjmr20212939

Abstract

Abstract:

Solid-state nuclear magnetic resonance (NMR) is an important technique to study the acidity and basicity of solid catalysts. Here we review some research works carried out in our laboratory, including studies on the acidity of metal oxides under different water contents, the acidity and basicity characterization of metal oxides by using acidic and basic probe molecules simultaneously. The investigations extend solid-state NMR technique in qualitative and quantitative studies on the acidity and basicity of solid catalysts.

Key words: solid-state nuclear magnetic resonance, adsorbed water molecules, acid-base probe molecules, acidity, basicity

CLC Number:

O643

Xin CHEN,Ying-yi FU,Bin YUE,He-yong HE. Acidity and Basicity of Solid Acid Catalysts Studied by Solid-State NMR[J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 491-502.

Figures/Tables 9

Fig.1

Fig.2

Table 1

Fig.3

Fig.4

Fig.5

Table 2

Fig.6

Fig.7

References 45

1	LERCHER J A , GRUNDLING C , EDER-MIRTH G . Infrared studies of the surface acidity of oxides and zeolites using adsorbed probe molecules[J]. Catal Today, 1996, 27 (3): 353- 376.
2	BUSCA G . Spectroscopic characterization of the acid properties of metal oxide catalysts[J]. Catal Today, 1998, 41 (1-3): 191- 206. doi: 10.1016/S0920-5861(98)00049-2
3	TOPSØE N Y , PEDERSEN K , DEROUANE E G . Infrared and temperature-programmed desorption study of the acidic properties of ZSM-5-type zeolites[J]. J Catal, 1981, 70 (1): 41- 52. doi: 10.1016/0021-9517(81)90315-8
4	HIDALGO C V , ITOH H , HATTORI T , et al. Measurement of the acidity of various zeolites by temperature-programmed desorption of ammonia[J]. J Catal, 1984, 85 (2): 362- 369. doi: 10.1016/0021-9517(84)90225-2
5	BROWN S P . Applications of high-resolution ¹H solid-state NMR[J]. Solid State Nucl Magn Reson, 2012, 41, 1- 27. doi: 10.1016/j.ssnmr.2011.11.006
6	HUNGER M . Brønsted acid sites in zeolites characterized by multinuclear solid-state NMR spectroscopy[J]. Catal Rev Sci Eng, 1997, 39 (4): 345- 393. doi: 10.1080/01614949708007100
7	ZHENG A M , HUANG S J , WANG Q , et al. Progress in development and application of solid-state NMR for solid acid catalysis[J]. Chin J Catal, 2013, 34 (3): 436- 491. doi: 10.1016/S1872-2067(12)60528-2
8	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.
	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.
9	HILL I M , HANSPAL S , YOUNG Z D , et al. DRIFTS of probe molecules adsorbed on magnesia, zirconia, and hydroxyapatite catalysts[J]. J Phys Chem C, 2015, 119 (17): 9186- 9197. doi: 10.1021/jp509889j
10	XU B Q , YAMAGUCHI T , TANABE K . Acid-base bifunctional behavior of ZrO₂ in dual adsorption of CO₂ and NH₃[J]. Chem Lett, 1988, (10): 1663- 1666.
11	YU Z W , ZHENG A M , WANG Q , et al. Acidity characterization of solid acid catalysts by solid-state NMR spectroscopy: A review on recent progresses[J]. Chinese J Magn Reson, 2010, 27 (4): 485- 515. doi: 10.3969/j.issn.1000-4556.2010.04.001
	喻志武, 郑安民, 王强, 等. 固体核磁共振研究固体酸催化剂酸性进展[J]. 波谱学杂志, 2010, 27 (4): 485- 515. doi: 10.3969/j.issn.1000-4556.2010.04.001
12	LI S H , HUANG S J , SHEN W L , et al. Probing the spatial proximities among acid sites in dealuminated H-Y zeolite by solid-state NMR spectroscopy[J]. J Phys Chem C, 2008, 112 (37): 14486- 14494. doi: 10.1021/jp803494n
13	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. doi: 10.1021/jacs.7b10940
14	YU Z W , ZHENG A M , WANG Q A , et al. Insights into the dealumination of zeolite HY revealed by sensitivity-enhanced ²⁷Al DQ-MAS NMR spectroscopy at high field[J]. Angew Chem Int Ed, 2010, 49 (46): 8657- 8661. doi: 10.1002/anie.201004007
15	SU X , XU S T , TIAN P , et al. Investigation of the strong Bronsted acidity in a novel SAPO-type molecular sieve, DNL-6[J]. J Phys Chem C, 2015, 119 (5): 2589- 2596. doi: 10.1021/jp511670q
16	ZHANG M Z , XU S T , LI J Z , et al. Methanol to hydrocarbons reaction over Hβ zeolites studied by high resolution solid-state NMR spectroscopy: Carbenium ions formation and reaction mechanism[J]. J Catal, 2016, 335, 47- 57. doi: 10.1016/j.jcat.2015.12.007
17	WANG Y , ZHUANG J Q , YANG G , et al. Study on the external surface acidity of MCM-22 zeolite: Theoretical calculation and ³¹P MAS NMR[J]. J Phys Chem B, 2004, 108 (4): 1386- 1391. doi: 10.1021/jp034989y
18	PENG Y K , YE L , QU J , et al. Trimethylphosphine-assisted surface fingerprinting of metal oxide nanoparticle by ³¹P solid-state NMR: A zinc oxide case study[J]. J Am Chem Soc, 2016, 138 (7): 2225- 2234. doi: 10.1021/jacs.5b12080
19	ZHENG A M , LI S H , LIU S B , et al. Acidic properties and structure-activity correlations of solid acid catalysts revealed by solid-state NMR spectroscopy[J]. Acc Chem Res, 2016, 49 (4): 655- 663. doi: 10.1021/acs.accounts.6b00007
20	LUNSFORD J H , ROTHWELL W P , SHEN W . Acid sites in zeolite Y: A solid-state NMR and infrared study using trimethylphosphine as a probe molecule[J]. J Am Chem Soc, 1985, 107 (6): 1540- 1547. doi: 10.1021/ja00292a015
21	LUNSFORD J H . Characterization of acidity in zeolites and related oxides using trimethylphosphine as a probe[J]. Top Catal, 1997, 4 (1-2): 91- 98.
22	ZHENG A M , LIU S B , DENG F . Acidity characterization of heterogeneous catalysts by solid-state NMR spectroscopy using probe molecules[J]. Solid State Nucl Magn Reson, 2013, 55, 12- 27.
23	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. doi: 10.1021/acs.chemrev.7b00289
24	OKUHARA T . Water-tolerant solid acid catalysts[J]. Chem Rev, 2002, 102 (10): 3641- 3666. doi: 10.1021/cr0103569
25	USHIKUBO T . Recent topics of research and development of catalysis by niobium and tantalum oxides[J]. Catal Today, 2000, 57 (3-4): 331- 338. doi: 10.1016/S0920-5861(99)00344-2
26	IGNATCHENKO A , NEALON D G , DUSHANE R , et al. Interaction of water with titania and zirconia surfaces[J]. J Mol Catal A: Chem, 2006, 256 (1-2): 57- 74. doi: 10.1016/j.molcata.2006.04.031
27	NOMA R , NAKAJIMA K , KAMATA K , et al. Formation of 5-(hydroxymethyl)furfural by stepwise dehydration over TiO₂ with water-tolerant Lewis acid sites[J]. J Phys Chem C, 2015, 119 (30): 17117- 17125. doi: 10.1021/acs.jpcc.5b03290
28	SANTOS K M A , ALBUQUERQUE E M , INNOCENTI G , et al. The role of Brønsted and water-tolerant Lewis acid sites in the cascade aqueous-phase reaction of triose to lactic acid[J]. Chem Cat Chem, 2019, 11 (13): 3054- 3063.
29	CHEN Z , ZHU G S , WU Y , et al. The promotion effect of transition metals on water-tolerant performance of Cu/SiO₂ catalysts in hydrogenation reaction[J]. Chemistry Select, 2019, 4 (48): 14063- 14068.
30	TAKAGAKI A . Rational design of metal oxide solid acids for sugar conversion[J]. Catalysts, 2019, 9 (11): 907. doi: 10.3390/catal9110907
31	NAKAJIMA K , BABA Y , NOMA R , et al. Nb₂O₅·nH₂O as a heterogeneous catalyst with water-tolerant Lewis acid sites[J]. J Am Chem Soc, 2011, 133 (12): 4224- 4227. doi: 10.1021/ja110482r
32	JIMENEZ-MORALES I , MORENO-RECIO M , SANTAMARIA-GONZALEZ J , et al. Mesoporous tantalum oxide as catalyst for dehydration of glucose to 5-hydroxymethylfurfural[J]. Appl Catal B: Environ, 2014, 154, 190- 196.
33	HIRUNSIT P , TOYAO T , SIDDIKI S , et al. Origin of Nb₂O₅ Lewis acid catalysis for activation of carboxylic acids in the presence of a hard base[J]. Chem Phys Chem, 2018, 19 (21): 2848- 2857. doi: 10.1002/cphc.201800723
34	HUANG F M , JIANG T Y , DAI H Y , et al. Transformation of glucose to 5-hydroxymethylfurfural over regenerated cellulose supported Nb₂O₅·nH₂O in aqueous solution[J]. Catal Lett, 2020, 150 (9): 2599- 2606. doi: 10.1007/s10562-020-03160-9
35	SKRODCZKY K , ANTUNES M M , HAN X Y , et al. Niobium pentoxide nanomaterials with distorted structures as efficient acid catalysts[J]. Commun Chem, 2019, 2, 129. doi: 10.1038/s42004-019-0231-3
36	LEAL G F , LIMA S , GRACA I , et al. Design of nickel supported on water-tolerant Nb₂O₅ catalysts for the hydrotreating of lignin streams obtained from lignin-first biorefining[J]. iScience, 2019, 15, 467- 488. doi: 10.1016/j.isci.2019.05.007
37	GUAN W X , CHEN X , JIN S H , et al. Highly stable Nb₂O₅-Al₂O₃ composites supported Pt catalysts for hydrodeoxygenation of diphenyl ether[J]. Ind Eng Chem Res, 2017, 56 (47): 14034- 14042. doi: 10.1021/acs.iecr.7b03736
38	HARA M . Heterogeneous Lewis acid catalysts workable in water[J]. Bull Chem Soc Jpn, 2014, 87 (9): 931- 941. doi: 10.1246/bcsj.20140131
39	BUNIAZET Z , COUBLE J , MAURY S , et al. Acidity of SiO₂-supported metal oxides in the presence of H₂O using the AEIR method: 2. Adsorption and coadsorption of NH₃ and H₂O on TiO₂/SiO₂ catalysts[J]. Langmui, 2020, 36 (45): 13383- 13395. doi: 10.1021/acs.langmuir.0c01717
40	CHEN X , HUANG D F , HE L L , et al. Effect of adsorbed water molecules on the surface acidity of niobium and tantalum oxides studied by MAS NMR[J]. J Phys Chem C, 2021, 125 (17): 9330- 9341. doi: 10.1021/acs.jpcc.1c02230
41	SHYLESH S , THIEL W R . Bifunctional acid-base cooperativity in heterogeneous catalytic reactions: advances in silica supported organic functional groups[J]. Chem Cat Chem, 2011, 3 (2): 278- 287.
42	WALLING C . The acid strength of surfaces[J]. J Am Chem Soc, 1950, 72 (3): 1164- 1168. doi: 10.1021/ja01159a025
43	VARTULI J C , SANTIESTEBAN J G , TRAVERSO P , et al. Characterization of the acid properties of tungsten/zirconia catalysts using adsorption microcalorimetry and n-pentane isomerization activity[J]. J Catal, 1999, 187 (1): 131- 138. doi: 10.1006/jcat.1999.2595
44	MOREL J P , MARMIER N , HUREL C , et al. Effect of temperature on the acid-base properties of the alumina surface: Microcalorimetry and acid-base titration experiments[J]. J Colloid Interface Sci, 2006, 298 (2): 773- 779. doi: 10.1016/j.jcis.2006.01.022
45	FU Y Y , ZHANG L , YUE B , et al. Simultaneous characterization of solid acidity and basicity of metal oxide catalysts via the solid-state NMR technique[J]. J Phys Chem C, 2018, 122 (42): 24094- 24102. doi: 10.1021/acs.jpcc.8b06827

催化剂	吸附模式	碱密度/(μmol·g^-1)				酸密度/(μmol·g^-1)
催化剂	吸附模式	强	中等	弱	总量	Lewis酸	Brønsted酸	总量
MgO	单吸附	-	10.5	-	10.5	-	-	-
	共吸附	3.6	6.9	6.7	17.2	15.8	-	15.8
ZrO₂	单吸附	0.1	8.9	6.0	15.0	108.5	2.8	111.3
	共吸附	0.8	13.0	6.0	19.8	65.0	10.8	75.8
Al₂O₃	单吸附	-	4.2	36.6	40.8	220.1	25.9	246.0
	共吸附	-	4.2	53.6	57.8	175.9	102.3	278.2

[1]	Han-di CHEN,Hai-yu KONG,Zhen-chao ZHAO,Wei-ping ZHANG. Exploring the Na⁺ Locations and Al Distributions in SSZ-39 Zeolite by Solid-State NMR Spectroscopy and DFT Calculations [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 543-551.
[2]	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.
[3]	Xi-feng XIA,Wen-jing ZHANG,Zhi-ye LIN,Xiao-kang KE,Yu-jie WEN,Fang WANG,Jun-chao CHEN,Lu-ming PENG. Solid-State NMR Studies on the Surface Structure and Properties of Oxide Nanomaterials [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 533-542.
[4]	Yong-xiang WANG,Qiang WANG,Jun XU,Qing-hua XIA,Feng DENG. The Effects of Ammonium Hexafluorosilicate Post-Treatment on the Acidity of H-ZSM-5 Zeolite Studied by Solid-State NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 514-522.
[5]	Zi-chun WANG,Jun HUANG,Yi-jiao JIANG. Solid-State NMR Spectroscopy Studies of Enhanced Acidity of Silica-Aluminas Based on Penta-Coordinated Aluminum Species [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 552-570.
[6]	Yao XIAO,Chang-jiu XIA,Xian-feng YI,Feng-qing LIU,Shang-bin LIU,An-min ZHENG. Progress in the Studies on Sn-Zeolites by Solid-State Nuclear Magnetic Resonance [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 571-584.
[7]	Shu-shu GAO,Shu-tao XU,Ying-xu WEI,Zhong-min LIU. Applications of Solid-State Nuclear Magnetic Resonance Spectroscopy in Methanol-to-Olefins Reaction [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 433-447.
[8]	LEI Zhen-yu, LIANG Xin-miao, LEI You-yi, YANG Li, FENG Ji-wen. Progresses in Solid-State NMR Studies on Carbon Anode Materials for Lithium/Sodium-Ion Batteries [J]. Chinese Journal of Magnetic Resonance, 2020, 37(1): 28-39.
[9]	WEI Ling, ZHANG Shan-min. Suppressing Background ¹³C NMR Signal From the Probe Head by Phase Incremented Pulses [J]. Chinese Journal of Magnetic Resonance, 2020, 37(1): 123-130.
[10]	LIN Ze-yu, HUO Hua, WANG Qi-hang. Progress in Solid-State NMR Studies of Monoclinic Lithium Vanadium Phosphate [J]. Chinese Journal of Magnetic Resonance, 2020, 37(1): 16-27.
[11]	WANG Jia-xin, FENG Ji-wen, CHEN Jun-fei, WANG Li-ying, LIU Chao-yang. Design and Fabrication of a Magic-Angle Spinning Rotor for Solid-State Nuclear Magnetic Resonance Probe [J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 446-455.
[12]	YAN Xiao-jing, HU Bing-wen. Probing ¹⁵N-¹⁵N Correlations in g-C₃N₄ Samples with Solid-State NMR SHA+ Pulse Sequence [J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 361-367.
[13]	YU Zhi-Wu, ZHENG An-Min, WANG Qiang, HUANG Shing-Jong, DENG Feng, LIU Shang-Bin. Acidity Characterization of Solid Acid Catalysts by Solid- State NMR Spectroscopy: A Review on Recent Progresses [J]. Chinese Journal of Magnetic Resonance, 2010, 27(4): 485-515.