YU Gui-yun1 , PENG Lu-ming2* . Solid-State NMR Studies of Layered Double Hydroxides: A Review[J]. Chinese Journal of Magnetic Resonance, 2015 , 32(2) : 228 -247 . DOI: 10.11938/cjmr20150207

[1] Martin K J, Pinnavaia T J. Layered double hydroxides as supported anionic reagents. Halide-ion reactivity in zinc chromium hexahydroxide halide hydrates [ Zn₂ Cr (OH) 6x.nH₂O](x = Cl, i)[J]. J Am Chem Soc, 1986, 108(3): 541－542.

[2] Cavani F, Trifirò F, Vaccari A. Hydrotalcite-type anionic clays: Preparation, properties and applications[J]. Catal Today, 1991, 11(2): 173－301.

[3] De Roy A, Forano C, Besse J. Layered double hydroxides: Synthesis and post-synthesis modification[J]. Layered Double Hydroxides: Present and Future, 2001: 1－39.

[4] He S, Zhao Y F, Wei M, et al. Fabrication of hierarchical layered double hydroxide framework on aluminum foam as a structured adsorbent for water treatment[J]. Ind Eng Chem Res, 2012, 51(1): 285－291.

[5] Torres-Rodríguez D A, Lima E, Valente J S, et al. CO2 capture at low temperatures (30–80 ℃) and in the presence of water vapor over a thermally activated Mg–Al layered double hydroxide[J]. J Phys Chem A, 2011, 115(44): 12 243－12 250.

[6] Morandi S, Manzoli M, Prinetto F, et al. Supported Ni catalysts prepared by intercalation of layered double hydroxides: Investigation of acid–base properties and nature of Ni phases[J]. Micropor Mesopor Mat, 2012, 147(1): 178－187.

[7] Primo A, Marino T, Corma A, et al. Efficient visible-light photocatalytic water splitting by minute amounts of gold supported on nanoparticulate CeO₂ obtained by a biopolymer templating method[J]. J Am Chem Soc, 2011, 133(18): 6 930－6 933.

[8] Zhang M C, Han D M, Lu C, et al. Organo-modified layered double hydroxides switch-on chemiluminescence[J]. J Phys Chem C, 2012, 116(10): 6 371－6 375.

[9] Shi W, Ji X, Zhang S, et al. Fluorescence chemosensory ultrathin films for Cd²⁺ based on the assembly of benzothiazole and layered double hydroxide[J]. J Phys Chem C, 2011, 115(42): 20 433－20 441.

[10] Shao M, Ning F, Zhao J, et al. Preparation of Fe3O4@SiO2@layered double hydroxide core-shell microspheres for magnetic separation of proteins[J]. J Am Chem Soc, 2012, 134(2): 1 071－1 077.

[11] Faour A, Mousty C, Prevot V, et al. Correlation among structure, microstructure, and electrochemical properties of NiAl–CO₃ layered double hydroxide thin films[J]. J Phys Chem C, 2012, 116(29): 15 646－15 659.

[12] Darder M, López-Blanco M, Aranda P, et al. Bio-nanocomposites based on layered double hydroxides[J]. Chem Mater, 2005, 17(8): 1 969－1 977.

[13] Sideris P J, Nielsen U G, Gan Z, et al. Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy[J]. Science, 2008, 321(5 885): 113－117.

[14] MacKenzie K J, Smith M E. Multinuclear Solid-State Nuclear Magnetic Resonance of Inorganic Materials[M]. Elsevier, 2002.

[15] Lesage A. Recent advances in solid-state NMR spectroscopy of spin I = 1/2 nuclei[J]. Phys Chem Chem Phys, 2009, 11(32): 6 876－6 891.

[16] Ashbrook S E. Recent advances in solid-state NMR spectroscopy of quadrupolar nuclei[J]. Phys Chem Chem Phys, 2009, 11(32): 6 892－6 905.

[17] Sutrisno A, Huang Y N. Multinuclear solid-state NMR and quantum chemical investigations of layered transition metal disulfides [J]. Chinese J Magn Reson, 2013, (4): 461－487.

[18] Marcelin G, Stockhausen N, Post J, et al. Dynamics and ordering of intercalated water in layered metal hydroxides[J]. J Phys Chem, 1989, 93(11): 4 646－4 650.

[19] Rey F, Fornés V, Rojo J M. Thermal decomposition of hydrotalcites. An infrared and nuclear magnetic resonance spectroscopic study[J]. J Chem Soc Faraday T, 1992, 88(15): 2 233－2 238.

[20] Van der Pol A, Mojet B, Van de Ven E, et al. Ordering of intercalated water and carbonate anions in hydrotalcite. An NMR study[J]. J Phys Chem, 1994, 98(15): 4 050－4 054.

[21] Reinholdt M X, Babu P K, Kirkpatrick R J. Proton dynamics in layered double hydroxides: A 1H T1 relaxation and line width investigation[J]. J Phys Chem C, 2009, 113(24): 10 623－10 631.

[22] Depège C, El Metoui F Z, Forano C, et al. Polymerization of silicates in layered double hydroxides[J]. Chem Mater, 1996, 8(4): 952－960.

[23] Aramendia M A, Borau V, Jimenez C, et al. Synthesis, characterization, and 1H and 71Ca MAS NMR spectroscopy of a novel Mg/Ga double layered hydroxide[J]. J Solid State Chem, 1997, 131(1): 78－83.

[24] Aramend??a M a A, Borau V, Jiménez C, et al. Xrd and 1H MAS NMR spectroscopic study of mixed oxides obtained by calcination of layered-double hydroxides[J]. Mater Lett, 2000, 46(6): 309－314.

[25] Combourieu B, Inacio J, Delort A M, et al. Differentiation of mobile and immobile pesticides on anionic clays by ¹H HR MAS NMR spectroscopy[J]. Chem Commun, 2001, (21): 2 214－2 215.

[26] Yesinowski J P, Eckert H. Hydrogen environments in calcium phosphates: Proton MAS NMR at high spinning speeds[J]. J Am Chem Soc, 1987, 109(21): 6 274－6 282.

[27] Cadars S, Layrac G, Gerardin C, et al. Identification and quantification of defects in the cation ordering in Mg/Al layered double hydroxides[J]. Chem Mater, 2011, 23(11): 2 821－2 831.

[28] Sideris P J, Blanc F, Gan Z, et al. Identification of cation clustering in Mg-Al layered double hydroxides using multinuclear solid state nuclear magnetic resonance spectroscopy[J]. Chem Mater, 2012, 24: 2 449－2 461.

[29] Petersen L B, Lipton A S, Zorin V, et al. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state 1H and 71Ga NMR spectroscopy[J]. J Solid State Chem, 2014, 219: 242－246.

[30] Yu G, Shen M, Wang M, et al. Probing local structure of layered double hydroxides with1h solid-state NMR spectroscopy on deuterated samples[J]. J Phys Chem Lett, 2014, 5(2): 363－369.

[31] He Y Y, Wang X M, Li F, et al. Determination of 1H-27Al dipolar coupling constant by 1H/27Al S-RESIDOR experiment under fast MAS[J]. Chinese J Magn Reson, 2013, 30(1): 93－102.

[32] Vyalikh A, Costa F R, Wagenknecht U, et al. From layered double hydroxides to layered double hydroxide-based nanocomposites- a solid-state NMR study[J]. J Phys Chem C, 2009, 113(51): 21 308－21 313.

[33] Reichle W, Kang S, Everhardt D. The nature of the thermal decomposition of a catalytically active anionic clay mineral[J]. J Catal, 1986, 101(2): 352－359.

[34] Beres A, Palinko I, Bertrand J C, et al. Dehydration-rehydration behaviour of layered double hydroxides: A study by X-ray diffractometry and MAS NMR spectroscopy[J]. J Mol Struct, 1997, 410: 13－16.

[35] Weir M R, Kydd R A. Synthesis of heteropolyoxometalate-pillared Mg/Al, Mg/Ga, and Zn/Al layered double hydroxides via ldh-hydroxide precursors[J]. Inorg Chem, 1998, 37(21): 5 619－5 624.

[36] Aramendía M A, Avilés Y, Borau V, et al. Thermal decomposition of Mg/Al and Mg/Ga layered-double hydroxides: A spectroscopic study[J]. J Mater Chem, 1999, 9(7): 1 603－1 607.

[37] del Arco M, Gutierrez S, Martin C, et al. Effect of the Mg:Al ratio on borate (or silicate)/nitrate exchange in hydrotalcite[J]. J Solid State Chem, 2000, 151(2): 272－280.

[38] Hou X, Kirkpatrick R J. Thermal evolution of the Cl-LiAl2 layered double hydroxide: A multinuclear MAS NMR and xrd perspective[J]. Inorg Chem, 2001, 40(25): 6 397－6 404.

[39] Prihod’ko R, Sychev M, Kolomitsyn I, et al. Layered double hydroxides as catalysts for aromatic nitrile hydrolysis[J]. Micropor Mesopor Mat, 2002, 56(3): 241－255.

[40] Hsueh H B, Chen C Y. Preparation and properties of LDHs/epoxy nanocomposites[J]. Polymer, 2003, 44(18): 5 275－5 283.

[41] Martínez-Ortiz M d J s, Lima E, Lara V, et al. Structural and textural evolution during folding of layers of layered double hydroxides[J]. Langmuir, 2008, 24(16): 8 904－8 911.

[42] Mackenzie K J D, Meinhold R H, Sherriff B L, et al. ²⁷Al and 25Mg solid-state magic-angle-spinning nuclear-magneticresonance study of hydrotalcite and its thermal-decomposition sequence[J]. J Mater Chem, 1993, 3(12): 1 263－1 269.

[43] Rocha J, del Arco M, Rives V, et al. Reconstruction of layered double hydroxides from calcined precursors: A powder xrd and ²⁷Al MAS NMR study[J]. J Mater Chem, 1999, 9(10): 2 499－2 503.

[44] Benito P, Labajos F M, Mafra L, et al. Carboxylate-intercalated layered double hydroxides aged under microwave-hydrothermal treatment[J]. J Solid State Chem, 2009, 182(1): 18－26.

[45] Vyalikh A, Massiot D, Scheler U. Structural characterisation of aluminium layered double hydroxides by ²⁷Al solid-state NMR[J]. Solid State Nucl Magn Reson, 2009, 36(1): 19－23.

[46] Ishihara S, Deguchi K, Sato H, et al. Multinuclear solid-state NMR spectroscopy of a paramagnetic layered double

hydroxide[J]. RSC Advances, 2013, 3(43): 19 857－19 860.

[47] Park T J, Choi S S, Kim Y. 27Al solid-state NMR structural studies of hydrotalcite compounds calcined at different temperatures[J]. Bull Korean Chem Soc, 2009, 30(1): 149.

[48] Zhan Y, Li D, Nishida K, et al. Preparation of “intelligent” pt/Ni/Mg (Al)O catalysts starting from commercial Mg–Al LDHs for daily start-up and shut-down steam reforming of methane[J]. Appl Clay Sci, 2009, 45(3): 147－154.

[49] Ueno S, Yoshida K, Ebitani K, et al. Hydrotalcite catalysis: Heterogeneous epoxidation of olefins using hydrogen peroxide in the presence of nitriles[J]. Chem Commun, 1998, (3): 295－296.

[50] Corma A, Navarro M, Pariente J P. Synthesis of an ultralarge pore titanium silicate isomorphous to MCM-41 and its application as a catalyst for selective oxidation of hydrocarbons[J]. J Chem Soc Chem Commun, 1994, (2): 147－148.

[51] Di Cosimo J, Apestegui&a C R, Gines M J L, et al. Structural requirements and reaction pathways in condensation reactions of alcohols on Mgy AlOx catalysts[J]. J Catal, 2000, 190(2): 261－275.

[52] Rao K K, Gravelle M, Valente J S, et al. Activation of Mg–Al hydrotalcite catalysts for aldol condensation reactions[J]. J Catal, 1998, 173(1): 115－121.

[53] Abelló S, Medina F, Tichit D, et al. Aldol condensations over reconstructed Mg-Al hydrotalcites: Structure–activity relationships related to the rehydration method[J]. Chem Eur J, 2005, 11(2): 728－739.

[54] Pfeiffer H, Lima E, Lara V, et al. Thermokinetic study of the rehydration process of a calcined MgAl-layered double hydroxide[J]. Langmuir, 2010, 26(6): 4 074－4 079.

[55] Griffin J M, Clark L, Seymour V R, et al. Ionothermal ¹⁷O enrichment of oxides using microlitre quantities of labelled water[J]. Chemical Science, 2012, 3(7): 2 293－2 300.

[56] Zhao L, Qi Z, Blanc F, et al. Investigating local structure in layered double hydroxides with ¹⁷O NMR spectroscopy[J]. Adv Funct Mater, 2014, 24(12): 1 696－1 702.

[57] Sahoo P, Ishihara S, Yamada K, et al. Rapid exchange between atmospheric CO₂ and carbonate anion intercalated within magnesium rich layered double hydroxide[J]. ACS Appl Mater Interfaces, 2014, 6(20): 18 352－18 359.

[58] Kozlova S G, Gabuda S P, Isupov V P, et al. Using NMR in structural studies of aluminum hydroxide intercalation compounds with lithium salts[J]. J Struct Chem, 2003, 44(2): 198－205.

[59] Velu S, Suzuki K, Okazaki M, et al. Synthesis of new Sn-incorporated layered double hydroxides and their thermal evolution to mixed oxides[J]. Chem Mater, 1999, 11(8): 2 163－2 172.

[60] Ay A N, Zümreoglu-Karan B, Temel A, et al. Layered double hydroxides with interlayer borate anions: A critical evaluation of synthesis methodology and ph-independent orientations in nano-galleries[J]. Appl Clay Sci, 2011, 51(3): 308－316.

[61] Fujii K, Hayashi S, Kodama H. Synthesis of an alkylammonium/magnesium phyllosilicate hybrid nanocomposite consisting of a smectite-like layer and organosiloxane layers[J]. Chem Mater, 2003, 15(5): 1 189－1 197.

[62] Wang G A, Wang C C, Chen C Y. The disorderly exfoliated LDHs/PMMA nanocomposite synthesized by in situ bulk polymerization[J]. Polymer, 2005, 46(14): 5 065－5 074.

[63] Reinholdt M X, Babu P K, Kirkpatrick R J. Preferential adsorption of lower-charge glutamate ions on layered double hydroxides: An NMR investigation[J]. J Phys Chem C, 2009, 113(9): 3 378－3 381.

[64] Pisson J, Morel-Desrosiers N, Morel J P, et al. Tracking the structural dynamics of hybrid layered double hydroxides[J]. Chem Mater, 2011, 23(6): 1 482－1 490.

[65] Sasaki S, Aisawa S, Hirahara H, et al. Synthesis of p-sulfonated calix [4] arene-intercalated layered double hydroxides and their adsorption properties for organic molecules[J]. J Eur Ceram Soc, 2006, 26(4): 655－659.

[66] Li Q, Kirkpatrick R J. Organic anions in layered double hydroxides: An experimental investigation of citrate hydrotalcite[J]. Am Mineral, 2007, 92(2-3): 397－402.

[67] Ishihara S, Sahoo P, Deguchi K, et al. Dynamic breathing of CO₂ by hydrotalcite[J]. J Am Chem Soc, 2013, 135(48): 18 040－18 043.

[68] Hou X Q, Kirkpatrick R J, Yu P, et al. 15N NMR study of nitrate ion structure and dynamics in hydrotalcite-like compounds[J]. Am Mineral, 2000, 85(1): 173－180.

[69] Park A Y, Kwon H, Woo A J, et al. Layered double hydroxide surface modified with (3‐aminopropyl) triethoxysilane by covalent bonding[J]. Adv Mater, 2005, 17(1): 106－109.

[70] Oh J M, Choi S J, Lee G E, et al. Inorganic drug delivery nanovehicle conjugated with cancer cell specific ligand[J]. Adv Funct Mater, 2009, 19(10): 1 617－1 624.

[71] Tao Q, Zhu J X, Frost R L, et al. Silylation of layered double hydroxides via a calcination-rehydration route[J]. Langmuir, 2010, 26(4): 2 769－2 773.

[72] Dong L, Ge C, Qin P, et al. Immobilization and catalytic properties of candida lipolytic lipase on surface of organic intercalated and modified MgAl-LDHs[J]. Solid State Sci, 2014, 31: 8－15.

[73] Hou X Q, Bish D L, Wang S L, et al. Hydration, expansion, structure, and dynamics of layered double hydroxides[J]. Am Mineral, 2003, 88(1): 167－179.

[74] Kirkpatrick R J, Yu P, Hou X Q, et al. Interlayer structure, anion dynamics, and phase transitions in mixed-metal layered hydroxides: Variable temperature 35Cl NMR spectroscopy of hydrotalcite and Ca-aluminate hydrate (hydrocalumite)[J]. Am Mineral, 1999, 84(7-8): 1 186－1 190.

[75] Hou, Kalinichev A G, Kirkpatrick R J. Interlayer structure and dynamics of Cl-LiAl2-layered double hydroxide: ³⁵Cl NMR observations and molecular dynamics modeling[J]. Chem Mater, 2002, 14(5): 2 078－2 085.

[76] Hou X, Kirkpatrick R J. Interlayer structure and dynamics of ClO₄ – layered double hydroxides[J]. Chem Mater, 2002, 14(3): 1 195－1 200.

[77] Hou X Q, Kirkpatrick R J. Solid-state 77Se NMR and xrd study of the structure and dynamics of seleno-oxyanions in hydrotalcite-like compounds[J]. Chem Mater, 2000, 12(7): 1 890－1 897.