Self Supported Synthesis of Porous Molybdenum-titanium Oxide and the Resulting Structural Transformation

doi:10.15541/jim20160069

Abstract

Abstract:

A series of porous molybdenum-titanium oxide (Mo-TiO₂) were prepared by mutual support of MoO₃ and TiO₂, and the resulting structural transformation with calcination temperature was also studied in the present study. The as-prepared samples were characterized mainly by XRD, BET, FESEM, and TG/DSC. When the calcination temperature was lower than 600℃, MoO₃ can maintain solid state. Mesoporous Mo-TiO₂ with surface area of 182 m²/g was obtained via mutual support of MoO₃ and TiO₂. The oxide loaded by more well-dispersed MoO₃ possessed significantly better hydrodesulfurization performance than that prepared by impregnation did. As MoO₃ was fused at above 600℃, “self supported effect” was disappeared and the porous structure of Mo-TiO₂ collapsed finally.

Key words: molybdenum-titanium oxide, self support, surface area, structural transformation, hydrodesulfurization

CLC Number:

TQ34

LI Li-Cheng, HE Tian-Tian, ZHAO Xue-Juan, QIAN Qi, WANG Lei, LI Xiao-Bao. Self Supported Synthesis of Porous Molybdenum-titanium Oxide and the Resulting Structural Transformation[J]. Journal of Inorganic Materials, 2016, 31(11): 1198-1204.

Figures/Tables 10

Table 1 Structural data of various porous molybdenum-titanium oxides

Samples	Crystalline phase	Crystalline particle size / nm^αα	Surface area / (m²·g^-1)	Pore volume / (cm³·g^-1)	Average pore size / nm	MoO₃ content / %
Titanate derivate	Amorphous	/	234	0.17	3.2	/
TiO₂	Anatase	8.6 ^A	103	0.20	5.9	/
Mo-TiO₂(400)	Anatase	4.7 ^A	182	0.14	3.7	16.1
Mo-TiO₂(500)	Anatase	6.2 ^A	173	0.21	4.9	14.0
Mo-TiO₂(600)	Anatase/rutile	14.1 ^A, 19.3 ^R	39	0.16	14.1	9.2
Mo-TiO₂(700)	Rutile	19.0 ^R	7.0	0.03	/	2.9
Mo-TiO₂(800)	Rutile	21.5 ^R	3.2	<0.01	/	2.5

Fig. 1 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of porous Mo-TiO2 with different calcination temperatures

Fig. 2 FESEM images of porous Mo-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

Fig. 3 Comparison on the surface area of Mo-TiO2 and TiO2 calcined at different temperatures

Fig. 4 Hydrodesulfurization performance of various porous Mo-TiO2

Fig. 5 XRD patterns of porous Mo-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

Fig. 6 XRD patterns of precursor Mo(I)-TiO2 calcined at different temperatures(a) 400℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) 800℃

Fig. 7 Peak height ratio of porous Mo-TiO2 composites

Fig. 8 TG and DSC curves of hybrid of ammonium molybdate and titanate derivative

Fig. 9 Scheme for preparation process of various porous Mo-TiO2 composites

References 33

[1]	RAMIREZ J, LUIS C, GUIDO B.The role of titania support in Mo-based hydrodesulfurization catalysts.Journal of Catalysis, 1999, 184(1): 59-67.
[2]	CHEN X B, SAMUEL S M.Titanium dioxide nanomaterials: synthesis, properties, modifications, and applications.Chemical Reviews, 2007, 107(7): 2891-2959.
[3]	DAHL M, LIU Y D, YIN Y D.Composite titanium dioxide nanomaterials. Chemical Reviews, 2014, 114(19): 9853-9889.
[4]	ZHANG H Z, BANFIELD J F.Understanding polymorphic phase transformation behavior during growth of nanocrystalline aggregates: insights from TiO2.The Journal of Physical Chemistry B, 2000, 104(15): 3481-3487.
[5]	HANAOR D A H, SORRELL C C. Review of the anatase to rutile phase transformation. Journal of Materials Science, 2011, 46(4): 855-874.
[6]	MOHAMMADI M R, FRAY D J, MOHAMMADI A.Sol-Gel nanostructured titanium dioxide: controlling the crystal structure, crystallite size, phase transformation, packing and ordering.Microporous and Mesoporous Materials, 2008, 112(1): 392-402.
[7]	ANTONELLI D M, JACKIE Y Y.Synthesis of hexagonally packed mesoporous TiO2 by a modified Sol-Gel method.Angewandte Chemie International Edition in English, 1995, 34(18): 2014-2017.
[8]	LEE D W, LEE K H.Novel eco-friendly synthesis of sucrose-templated mesoporous titania with high thermal stability.Microporous and Mesoporous Materials, 2011, 142(1): 98-103.
[9]	JUNG J H, HIDEKI K, KJELD J C B, et al. Creation of novel helical ribbon and double-layered nanotube TiO2 structures using an organogel template.Chemistry of Materials, 2002, 14(4): 1445-1447.
[10]	KASUGA T, MASAYOSHI H, AKIHIKO H, et al.Formation of titanium oxide nanotube.Langmuir, 1998, 14(12): 3160-3163.
[11]	CORTES J M A, ESCOBAR J, ANGELES C, et al. Highly dispersed CoMoS phase on titania nanotubes as efficient HDS catalysts.Catalysis Today, 2008, 130(1): 56-62.
[12]	DZWIGAJ S, LOUIS C, BREYSSE M, et al.New generation of titanium dioxide support for hydrodesulfurization.Applied Catalysis B: Environmental, 2003, 41(1): 181-191.
[13]	INOUE S, AKIHIRO M, HIDEHIKO K, et al.Preparation of novel titania support by applying the multi-gelation method for ultra- deep HDS of diesel oil.Applied Catalysis A: General, 2004, 269(1): 7-12.
[14]	HE M, LU X H, FENG X, et al. A simple approach to mesoporous fibrous titania from potassium dititanate.Chemical Communications, 2004(19): 2202-2203.
[15]	OKADA K, NOBUO Y, YOSHIKAZU K, et al.Effect of silica additive on the anatase-to-rutile phase transition.Journal of the American Ceramic Society, 2001, 84(7): 1591-1596.
[16]	YANG J, HUANG Y X, Ferreira J M F. Inhibitory effect of alumina additive on the titania phase transformation of a Sol--Gel-derived powder.Journal of Materials Science Letters, 1997, 16(23): 1933-1935.
[17]	ZHANG J, Li M J, FENG Z C, et al.UV Raman spectroscopic study on TiO2. I. phase transformation at the surface and in the bulk.The Journal of Physical Chemistry B, 2006, 110(2): 927-935.
[18]	YUAN C Z, ZHOU L, HOU L R.Facile fabrication of self-supported three-dimensional porous reduced graphene oxide film for electrochemical capacitors.Materials Letters, 2014, 124: 253-255.
[19]	WANG Z, Chen G, DING K.Self-supported catalysts. Chemical Reviews, 2008, 109(2): 322-359.
[20]	MAKWANA N M, RAUL Q C, PARKIN I P, et al.A simple and low-cost method for the preparation of self-supported TiO2-WO3 ceramic heterojunction wafers. Journal of Materials Chemistry A, 2014, 2(41): 17602-17608.
[21]	SUN J B, LI B, CAI K P, et al.TiO2 Photolysis device fabricated by direct ink write assembly.Journal of Inorganic Materials, 2011, 26(3): 300-304.
[22]	SPURR R A, HOWARD M.Quantitative analysis of anatase-rutile mixtures with an X-ray diffractometer.Analytical Chemistry, 1957, 29(5): 760-762.
[23]	SHENG Q R, YUAN S, ZHANG J L, et al.Synthesis of mesoporous titania with high photocatalytic activity by nanocrystalline particle assembly.Microporous and Mesoporous Materials, 2006, 87(3): 177-184.
[24]	LI L C, WANG Y F, SHI K Z, et al.Preparation and characterization of mesoporous MoO3/TiO2 composite with high surface area by self-Supporting and ammonia method.Catalysis Letters, 2012, 142: 480-485.
[25]	ZHANG J, XU Q, FENG Z C, et al.Importance of the relationship between surface phases and photocatalytic activity of TiO2.Angewandte Chemie International Edition in English, 2008, 47(9): 1766-1769.
[26]	LI W, BAI Y, LIU C, et al.Highly thermal stable and highly crystalline anatase TiO2 for photocatalysis.Environmental Science & Technology, 2009, 43(14): 5423-5428.
[27]	SONG R Q, XU A W, DENG B, et al.Novel multilamellar mesostructured molybdenum oxide nanofibers and nanobelts: synthesis and characterization.The Journal of Physical Chemistry B, 2005, 109(48): 22758-22766.
[28]	BADICA P.Preparation through the vapor transport and growth mechanism of the first-order hierarchical structures of MoO3 belts on sillimanite fibers.Crystal growth & design, 2007, 7(4): 794-801.
[29]	ONO T, KAMISUKI H, HISASHI H, et al.A comparison of oxidation activities and structures of Mo oxides highly dispersed on group IV oxide supports.Journal of Catalysis, 1989, 116(1): 303-307.
[30]	THORNE A, KRUTH A, TUNSTALL D, et al.Formation, structure, and stability of titanate nanotubes and their proton conductivity.The Journal of Physical Chemistry B, 2005, 109(12): 5439-5444.
[31]	SHAHEEN W M, SELIM M M.Thermal decompositions of pure and mixed manganese carbonate and ammonium molybdate tetrahydrate.Journal of Thermal Analysis and Calorimetry, 2000, 59(3): 961-970.
[32]	ZENG T, BAI Y, LI H, et al.Preparation of polyhedral copper oxide nanoparticles by molten-salt method and their catalytic performance.Journal of Inorganic Materials, 2015, 30(4): 439-442.
[33]	WU X, LI H F, ZHOU J L, et al.Fabrication and properties of highly pure BiFeO3 using a method of solid state reaction-molten salt synthesis with non-equilibrium Process. Journal of Inorganic Materials, 2014, 29(11): 1151-1155.