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

doi:10.11938/cjmr20202818

摘要/Abstract

摘要： 本文利用原位液体核磁共振技术对真实固液体系光催化甲醇重整过程中水与甲醇之间的相互作用进行了系统性研究，证实了甲醇+水体系中氢键及质子交换相互作用的存在，并且发现催化剂的种类（包括不同晶型，以及同一晶型、不同形貌的TiO₂）、体系温度、光照反应条件都会影响甲醇与水之间的相互作用，进而影响到甲醇重整的效率．这表明催化剂及温度的合适选择对于提升甲醇重整效率起到非常重要的作用．

关键词: 原位核磁共振(NMR), 甲醇重整, 光催化, 液体核磁共振

Abstract: In this work, an operando NMR method was used to investigate the interaction between water and methanol in photocatalytic methanol reforming process in a real solid-liquid environment. The existence of hydrogen bonding and proton exchange between water and methanol were proven. The experimental results demonstrated that, the interaction between methanol and water is affected by the type of catalyst, reaction temperature and light irradiation, which consequently influences the methanol reforming efficiency. It was also shown that selection of the appropriate temperature and catalyst could improve methanol reforming efficiency.

Key words: operando nuclear magnetic resonance (NMR), methanol reforming, photocatalysis, liquid-state nuclear magnetic resonance

中图分类号:

O482.53

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.

WANG Rui-di, XU Bei-bei, SONG Yan-hong, WANG Xue-lu, YAO Ye-feng. Methanol-Water Interaction in Photocatalytic Methanol Reforming ─ An Operando NMR Study[J]. Chinese Journal of Magnetic Resonance, 2021, 38(1): 43-57.

参考文献

[1] CUI Y J, DING Z X, FU X Z, et al. Construction of conjugated carbon nitride nanoarchitectures in solution at low temperatures for photoredox catalysis[J]. Angew Chem Int Edit, 2012, 51(47):11814-11818.
[2] DONG F, LI Y H, WANG Z Y, et al. Enhanced visible light photocatalytic activity and oxidation ability of porous graphene-like g-C3N4 nanosheets via thermal exfoliation[J]. Appl Surf Sci, 2015, 358:393-403.
[3] LWIN Y, DAUD W R W, MOHAMAD A B, et al. Hydrogen production from steam-methanol reforming:thermodynamic analysis[J]. Int J Hydrogen Energ, 2000, 25(1):47-53.
[4] RAMESHAN C, WEILACH C, STADLMAYR W, et al. Steam reforming of methanol on PdZn near-surface alloys on Pd (111) and Pd foil studied by in-situ XPS, LEIS and PM-IRAS[J]. J Catal, 2010, 276(1):101-113.
[5] MIYAO T, YAMAUCHI M, NAITO S. Liquid phase methanol reforming with water over silica supported Pt-Ru catalysts[J]. Catal Today, 2003, 87(1-4):227-235.
[6] FUJISHIMA A, HONDA K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238(5358):37-38.
[7] KAWAI T, SAKATA T. Photocatalytic hydrogen production from liquid methanol and water[J]. J Chem Soc, Chem Commun, 1980, 15:694-695.
[8] KUDO A. Photocatalyst materials for water splitting[J]. Catal Surv Asia, 2003, 7(1):31-38.
[9] WANG X L, LIU W Q, YU Y Y, et al. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions[J]. Nat Commun, 2016, 7(1):1-7.
[10] 叶曼.原位核磁共振技术探究液态环境中甲醇光催化重整反应机理[D].上海:华东师范大学, 2019.
[11] XU C B, YANG W S, GUO Q, et al. Photoinduced decomposition of formaldehyde on a TiO₂(110) surface, assisted by bridge-bonded oxygen atoms[J]. J Phys Chem Lett, 2013, 4(16):2668-2673.
[12] WANG T J, HAO Q Q, WANG Z Q, et al. Deuterium kinetic isotope effect in the photocatalyzed dissociation of methanol on TiO₂(110)[J]. J Phys Chem C, 2018, 122(46):26512-26518.
[13] XU C B, YANG W S, GUO Q, et al. Molecular hydrogen formation from photocatalysis of methanol on anatase-TiO₂(101)[J]. J Am Chem Soc, 2014, 136(2):602-605.
[14] BENNETT D A, CARGNELLO M, GORDON T R, et al. Thermal and photochemical reactions of methanol on nanocrystalline anatase TiO₂ thin films[J]. Phys Chem Chem Phys, 2015, 17(26):17190-17201.
[15] BANFIELD J F, VEBLEN D R, SMITH D J. The identification of naturally occurring TiO₂(B) by structure determination using high-resolution electron microscopy, image simulation, and distance-least-squares refinement[J]. Am Mineral, 1991, 76(3/4):343-353.
[16] ASAHI R, TAGA Y, MANNSTADT W, et al. Electronic and optical properties of anatase TiO₂[J]. Phys Rev B, 2000, 61(11):7459.
[17] MATSUI M, AKAOGI M. Molecular dynamics simulation of the structural and physical properties of the four polymorphs of TiO₂[J]. Mol Simulat, 1991, 6(4-6):239-244.
[18] GRANT F A. Properties of rutile (titanium dioxide)[J]. Rev Mod Phys, 1959, 31(3):646.
[19] DYLLA A G, HENKELMAN G, STEVENSON K J. Lithium insertion in nanostructured TiO₂(B) architectures[J]. Accounts Chem Res, 2013, 46(5):1104-1112.
[20] WILKENING M, HEINE J, LYNESS C, et al. Li diffusion properties of mixed conducting TiO₂-B nanowires[J]. Phys Rev B, 2009, 80(6):064302.
[21] KUO H L, KUO C Y, LIU C H, et al. A highly active bi-crystalline photocatalyst consisting of TiO₂(B) nanotube and anatase particle for producing H₂ gas from neat ethanol[J]. Catal Lett, 2007, 113(1/2):7-12.
[22] SANCHES F F, MALLIA G, HARRISON N M. Simulating constant current STM images of the rutile TiO₂(110) surface for applications in solar water splitting[J]. Mater Res Soc Symp Proc, 2013, 1494:339-344.
[23] CHEN T, FENG Z C, WU G P, 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.
[24] HERMAN G S, DOHNALEK Z, RUZYCKI N, et al. Experimental investigation of the interaction of water and methanol with anatase− TiO₂(101)[J]. J Phys Chem B, 2003, 107(12):2788-2795.
[25] ZHOU C Y, REN Z F, MA Z B, et al. Photochemistry of Methanol on TiO₂(110)[C]//Conference on molecular energy transfer. Oxford, UK:2011, 44-0.
[26] SCHLEGEL S J, HOSSEINPOUR S, GEBHARD M, et al. How water flips at charged titanium dioxide:an SFG-study on the water-TiO₂ interface[J]. Phys Chem Chem Phys, 2019, 21(17):8956-8964.
[27] LANG X F, LIANG Y H, SUN L L, et al. Interplay between methanol and anatase TiO₂(101) surface:The effect of subsurface oxygen vacancy[J]. J Phys Chem C, 2017, 121(11):6072-6080.
[28] BERARDO E, HU H S, VAN DAM H J J, et al. Describing excited state relaxation and localization in TiO₂nanoparticles using TD-DFT[J]. J Chem Theory Comput, 2014, 10(12):5538-5548.
[29] ZHANG H M, YU X H, MCLEOD J A, et al. First-principles study of Cu-doping and oxygen vacancy effects on TiO₂ for water splitting[J]. Chem Phys Lett, 2014, 612:106-110.
[30] LIU W Q, SONG Y H, WANG X L, et al. In operando nuclear magnetic resonance spectroscopy study on photocatalytic methanol reforming[J]. Chinese J Magn Reson, 201936(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, 201936(3):298-308.
[31] 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.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.