Probing Framework Boron Speciation and Spatial Distribution in MFI Zeolites by Solid-state NMR

Abstract

This study utilizes advanced solid-state NMR spectroscopy to elucidate the spatial distribution, coordination behavior, and inter-nuclear interactions of boron species in B-MFI zeolites. Through ¹³C-{¹¹B} symmetry-based resonance-echo saturation-pulse double-resonance (S-RESPDOR) NMR experiment, we reveal that boron incorporation is preferentially directed by tetrapropylammonium (TPA⁺) structure-directing agents, with boron predominantly occupying both sinusoidal and straight channels rather than channel intersections. Quantitative analysis further indicates a closer proximity to terminal methyl groups of TPA⁺ in sinusoidal channels (B-C_γ′: ca. 2.8 Å) (1 Å=0.1 nm) compared to straight channels (B-C_γ: ca. 3.1 Å). Upon dehydration, two-dimensional (2D) ¹¹B multiple-quantum magic-angle spinning (MQMAS) NMR, together with a 2D ¹H-{¹¹B} dipolar-based heteronuclear multiple quantum correlation (D-HMQC) experiment, identifies two distinct trigonal boron species, attributed to framework boron perturbed by proximal silanols, highlighting microenvironmental heterogeneity. Our findings establish that boron siting is template-directed and that dehydration induces distinct speciation, providing atomic-scale insights that are crucial for the rational design of zeolites.

Keywords

Borosilicate zeolite / MFI topology / Solid-state NMR / Internuclear distance / Boron speciation

References

[1] Liu L, Lu J, Yang Y, Ruettinger W, Gao X, Wang M, Lou H, Wang Z, Liu Y, Tao X, Li L, Wang Y, Li H, Zhou H, Wang C, Luo Q, Wu H, Zhang K, Ma J, Cao X, Wang L, Xiao F-SScience, 2024, 383: 94.

[2] Sun Q, Xie Z, Yu JNatl. Sci. Rev., 2017, 5: 542.

[3] Vermeiren W, Gilson JTop. Catal., 2009, 52: 1131.

[4] Gao P, Wang Q, Xu J, Qi G, Wang C, Zhou X, Zhao X, Feng N, Liu X, Deng FACS Catal., 2018, 8: 69.

[5] Cheng K, Smulders L C J, van der Wal L I, Oenema J, Meeldijk J D, Visser N L, Sunley G, Roberts T, Xu Z, Doskocil E, Yoshida H, Zheng Y, Zecevic J, de Jongh P E, de Jong K PScience, 2022, 377: 204.

[6] Tian H, Li W, He L, Zhong Y, Xu S, Xiao H, Xu BNat. Commun., 2023, 14: 6520.

[7] Zhang L, Liu N, Dai C, Xu R, Yu G, Chen B, Wang NChem. Synth., 2023, 3: 2.

[8] Hao J, Zhou J, Wang Y, Li L, Sheng Z, Teng J, Xie ZChem Catal., 2024, 4: 101041

[9] He L-H, Li J-J, Han S-Y, Fan D, Li X-J, Xu S-T, Wei Y-X, Liu Z-MChem. Synth., 2024, 4: 1.

[10] Wang X, Wu X, Zhao M, Zhang R, Wang Z, Li Y, Zhang L, Wang X, Song S, Zhang HNano Res., 2024, 17: 5645.

[11] Zhang L, Li T, Xiang W, Ye Z, Wu L, Xia W, Huang H, Liu Z, Jiang X, Liu G, Jin Z, Gao W, Li H, Zeng J, Tsubaki NJ. Am. Chem. Soc., 2025

[12] Deruiter R, Kentgens A, Grootendorst J, Jansen J, Vanbekkum HZeolites, 1993, 13: 128.

[13] Taniguchi T, Yoneta K, Nakaoka S, Nakasaka Y, Yokoi T, Tago T, Masuda TCatal. Lett., 2016, 146: 442.

[14] Xu W, Su J, Ni X, Yang Q, Song W, Wang L, Zhu HChem. Commun., 2024, 60: 5751.

[15] Li G, Foo C, Fan R, Zheng M, Wang Q, Chu Y, Li J, Day S, Steadman P, Tang C, Lo T W B, Deng F, Tsang S C EScience, 2025, 387: 388.

[16] Stave M S, Nicholas J BJ. Phys. Chem., 1995, 99: 15046.

[17] Millini R, Perego G, Bellussi GTop. Catal., 1999, 9: 13.

[18] Hwang S-J, Chen C-Y, Zones S IJ. Phys. Chem. B, 2004, 108: 18535.

[19] Wiper P, Amelse J, Mafra LJ. Catal., 2014, 316: 240.

[20] Fild C, Eckert H, Koller HAngew. Chem. Int. Ed., 1998, 37: 2505.

[21] Fild C, Eckert H, Koller HJ. Am. Chem. Soc., 2000, 122: 12590.

[22] Fild C, Shantz D F, Lobo R F, Koller HPhys. Chem. Chem. Phys., 2000, 2: 3091.

[23] Trudu F, Tabacchi G, Gamba A, Fois EJ. Phys. Chem. C, 2008, 112: 15394.

[24] Chu C T W, Kuehl G H, Lago R M, Chang C DJ. Catal., 1985, 93: 451.

[25] Coudurier G, Auroux A, Vedrine J C, Farlee R D, Abrams L, Shannon R DJ. Catal., 1987, 108: 1.

[26] Heitmann G, Dahlhoff G, Niederer J, Hölderich WJ. Catal., 2000, 194: 122.

[27] Wang K, Wang F, Zhai Y, Wang J, Zhang X, Li M, Jiang L, Fan X, Bing C, Zhang J, Zhang XMol. Catal., 2023, 535: 112881

[28] Mi Z, Lu T, Zhang J, Xu R, Yan WChem. Res. Chinese Universities, 2022, 38: 9.

[29] Bo S, Wang T, Lv T, Wu H, Feng Z, Miao L, Feng Z, Ren L, Meng CChem. Res. Chinese Universities, 2024, 40: 1245.

[30] Du K, Zhang X, He T, Shen W, Xu H, Tang Y, Cao X, Huang Z, Zhang YAngew. Chem. Int. Ed., 2025, 64: e202507223.

[31] Liu M, Guo X, Gao J, Wang X, Liu X, Han X, Bao XChin. J. Catal., 2005, 26: 660

[32] Li J, Zhang Z, Li X, Bao S, Liu L, He H, Lai X, Zhang L, Zhang PIntegr. Ferroelectr., 2018, 189: 165.

[33] Sun B, Kang Y, Shi Q, Arowo M, Luo Y, Chu G, Zou HCan. J. Chem. Eng., 2019, 97: 3063.

[34] Tai W, Dai W, Wu G, Li LChem. Synth., 2023, 3: 38.

[35] Simancas R, Dari D, Velamazán N, Navarro M T, Cantín A, Jordá J L, Sastre G, Corma A, Rey FScience, 2010, 330: 1219.

[36] Liu X, Yan N, Ma C, Wang L, Tian P, Guo P, Liu ZInorg. Chem. Commun., 2021, 126: 108467.

[37] Zhou H, Yi X, Hui Y, Wang L, Chen W, Qin Y, Wang M, Ma J, Chu X, Wang Y, Hong X, Chen Z, Meng X, Wang H, Zhu Q, Song L, Zheng A, Xiao FScience, 2021, 372: 76.

[38] Yaripour F, Shariatinia Z, Sahebdelfar S, Irandoukht AMicroporous Mesoporous Mater., 2015, 203: 41.

[39] Coudurier G, Auroux A, Vedrine J, Farlee R, Abrams L, Shannon RJ. Catal, 1987, 108: 1.

[40] Lanzafame P, Papanikolaou G, Perathoner S, Centi G, Migliori M, Catizzone E, Aloise A, Giordano GCatal. Sci. Technol., 2018, 8: 1304.

[41] Mortlock R, Bell A, Radke CJ. Phys. Chem., 1991, 95: 372.

[42] Sanhoob M, Muraza O, Shafei E, Yokoi T, Choi KAppl. Catal. B Environ., 2017, 210: 432.

[43] Zhu Q, Takiguchi M, Setoyama T, Yokoi T, Kondo J, Tatsumi TCatal. Lett., 2011, 141: 670.

[44] Grosskreuz I, Gies H, Marler BMicroporous Mesoporous Mater., 2020, 291: 109683.

[45] Hur Y, Kester P, Nimlos C, Cho Y, Miller J, Gounder RInd. Eng. Chem. Res., 2019, 58: 11849.

[46] Hamidzadeh M, Nazari M, Shifteh S, Abdolali AMicroporous Mesoporous Mater., 2025, 381: 113344.

[47] Wang Y, Zeng S, Wang P, Zheng M, Huang W, Chu Y, Feng N, Qi G, Wang Q, Xu J, Deng FMagnetic Resonance Letters, 2025, 5: 200174.

[48] Sundaramurthy V, Lingappan NBull. Chem. Soc. Jpn., 2001, 73: 341.

[49] de R R, Jansen J C, van Bekkum HZeolites, 1992, 12: 56.

[50] Bandyopadhyay R, Kubota Y, Sugimoto N, Fukushima Y, Sugi YMicroporous Mesoporous Mater., 1999, 32: 81.

[51] Li S, Lafon O, Wang W, Wang Q, Wang X, Li Y, Xu J, Deng FAdv. Mater., 2020, 32: 2002879.

[52] Qi G, Wang Q, Xu J, Deng FChem. Soc. Rev., 2021, 50: 8382.

[53] Axon S, Klinowski JJ. Phys. Chem., 1994, 98: 1929.

[54] Hough A, Routh A, Clarke S, Wiper P, Amelse J, Mafra LJ. Catal., 2016, 334: 14.

[55] Zheng M, Chu Y, Wang Q, Wang Y, Xu J, Deng FProgress in Nuclear Magnetic Resonance Spectroscopy, 2024, 140: 1.

[56] Zhao X, Xu J, Chu Y, Qi G, Wang Q, Gao W, Li S, Feng N, Deng FChemcatchem, 2020, 12: 3880.

[57] Xin S, Wang Q, Xu J, Chu Y, Wang P, Feng N, Qi G, Trébosc J, Lafon O, Fan W, Deng FChem. Sci., 2019, 10: 10159.

[58] Li C, Vidal-Moya A, Miguel P, Dedecek J, Boronat M, Corma AACS Catalysis, 2018, 8: 7688.

[59] Gabelica Z, Nagy J B, Bodart P, Debras GChem. Lett., 2006, 13: 1059.

[60] Gabelica Z, Nagy J B, Debras GStud. Surf. Sci. Catal., 1984, 19: 113.

[61] Fyfe C A, Gobbi G C, Klinowski J, Thomas J M, Ramdas SNature, 1982, 296: 530.

[62] Kokotailo G T, Lawton S L, Olson D H, Meier W MNature, 1978, 272: 437.

[63] Moliner M, Rey F, Corma AAngew. Chem. Int. Ed., 2013, 52: 13880.

[64] Price G, Pluth J, Smith J, Bennett J, Patton RJ. Am. Chem. Soc., 1982, 104: 5971.

[65] Abraham A, Prins R, van Bokhoven J, van Eck E, Kentgens ASolid State Nucl. Magn. Reson., 2009, 35: 61.

[66] Chen L, Wang Q, Hu B, Lafon O, Trébosc J, Deng F, Amoureux JPhys. Chem. Chem. Phys., 2010, 12: 9395.

[67] Lu X, Lafon O, Trébosc J, Amoureux JJ. Magn. Reson., 2012, 215: 34.

[68] Dib E, Grand J, Gedeon A, Mintova S, Fernandez CMicroporous Mesoporous Mater., 2021, 315: 110899.

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