Modified iron-molybdate catalysts with various metal oxides by a mechanochemical method: enhanced formaldehyde yield in methanol partial oxidation

Abstract

A mechanochemical method was employed to prepare modified iron molybdate catalysts with various metal salts as precursors. The physicochemical properties of the iron molybdate catalysts were characterized, and their performances in catalyzing the reaction from methanol to formaldehyde (HCHO) were evaluated. Iron molybdate catalysts doped with Co(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O resulted in high HCHO yields. Compared with a commercial catalyst, the HCHO yields in the reaction with the modified catalyst at an optimal Co/Mo molar ratio reached 97.37%. According to chemical state analysis, the formation of CoO and the efficient decrease in the MoO₃ sublimation rate could be important factors enhancing the HCHO yield in reactions catalyzed with iron molybdate doped with different Co/Mo mole ratios.

Graphical abstract

Keywords

iron molybdate catalyst / metal oxides / methanol to formaldehyde / Co/Mo ratio / formaldehyde yield

References

[1] Heim L E, Konnerth H, Prechtl M H G. Future perspectives for formaldehyde: pathways for reductive synthesis and energy storage. Green Chemistry, 2017, 19(10): 2347–2355

[2] Yeo B R, Pudge G J F, Bugler K G, Rushby A V, Kondra S, Bartley J, Golunsk S, Taylor S H, Gibson E, Wells P P, . The surface of iron molybdate catalysts used for the selective oxidation of methanol. Surface Science, 2016, 648: 163–169

[3] Deshmukh S A R K, Annaland M V S, Kuipers J A M. Kinetics of the partial oxidation of methanol over a Fe-Mo catalyst. Applied Catalysis A, General, 2005, 289(2): 240–255

[4] Raun K V, Thorhauge M, Høj M, Jensen A D. Modeling of molybdenum transport and pressure drop increase in fixed bed reactors used for selective oxidation of methanol to formaldehyde using iron molybdate catalysts. Chemical Engineering Science, 2019, 202: 347–356

[5] Soares A P V, Portela M F, Kiennemann A. Methanol selective oxidation to formaldehyde over iron-molybdate catalysts. Catalysis Reviews. Science and Engineering, 2015, 47: 125–174

[6] Brookes C, Bowker M, Wells P P. Catalysts for the selective oxidation of methanol. Catalysts, 2016, 6(92): 1–27

[7] Xiao Y, Wang Y, Varma A. Low-temperature selective oxidation of methanol over Pt-Bi bimetallic catalysts. Journal of Catalysis, 2018, 363: 144–153

[8] Braz C G, Mendes A, Rocha J, Alvim R, Matos H A. Model of an industrial multitubular reactor for methanol to formaldehyde oxidation in the presence of catalyst deactivation. Chemical Engineering Science, 2019, 195: 347–355

[9] Raun K V, Johannessen J, McCormack K, Appel C C, Baier S, Thorhauge M, Høj M, Jensen A D. Modeling of the molybdenum loss in iron molybdate catalyst pellets for selective oxidation of methanol to formaldehyde. Chemical Engineering Journal, 2019, 361: 1285–1295

[10] Dehnamaki H, Iranshahi D. Simultaneous synthesis and oxidation of methanol to formaldehyde thermally coupled with cyclohexane dehydrogenation in a trifunctional reactor. Energy & Fuels, 2019, 33: 4487–4498

[11] Deng X Y, Sorescu D C, Lee J. Methanol oxidation to formaldehyde promoted at the step sites of ultrathin ZnO. Topics in Catalysis, 2018, 61: 499–508

[12] Soares A P V, Portela M F, Kiennemann A, Hilaire L. Mechanism of deactivation of iron-molybdate catalysts prepared by coprecipitation and sol-gel techniques in methanol to formaldehyde oxidation. Chemical Engineering Science, 2003, 58(7): 1315–1322

[13] Raun K V, Lundegaard L F, Chevallier J, Beato P, Appel C C, Nielsen K, Thorhauge M, Jensen A D, Høj M. Deactivation behavior of an iron-molybdate catalyst during selective oxidation of methanol to formaldehyde. Catalysis Science & Technology, 2018, 8: 4626–4637

[14] House M P, Carley A F, Bowker M. Selective oxidation of methanol on iron molybdate catalysts and the effects of surface reduction. Journal of Catalysis, 2007, 252: 88–96

[15] Routray K, Zhou W, Kiely C J, Grünert W, Wachs I E. Origin of the synergistic interaction between MoO₃ and iron molybdate for the selective oxidation of methanol to formaldehyde. Journal of Catalysis, 2010, 275: 84–98

[16] Brookes C, Wells P P, Cibin G, Dimitratos N, Jones W, Morgan D J, Bowker M. Molybdenum oxide on Fe₂O₃ core-shell catalysts: probing the nature of the structural motifs responsible for methanol oxidation catalysis. ACS Catalysis, 2013, 4: 243–250

[17] Choksi T, Greeley J. Partial oxidation of methanol on MoO₃ (010): a DFT and microkinetic study. ACS Catalysis, 2016, 6(11): 7260–7277

[18] Niu J T, Liland S E, Yang J, Rout K R, Ran J Y, Chen D. Effect of oxide additives on the hydrotalcite derived Ni catalysts for CO₂ reforming of methane. Chemical Engineering Journal, 2019, 377: 119763–119775

[19] Ma Z, Overbury S H, Dai S. Au/M_xO_y/TiO₂ catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives. Journal of Molecular Catalysis A Chemical, 2007, 273(1-2): 186–197

[20] Gu S, Oh H, Choi J W, Suh D J, Jae J, Choi J, Ha J. Effects of metal or metal oxide additives on oxidative coupling of methane using Na₂WO₄/SiO₂ catalysts: reducibility of metal additives to manipulate the catalytic activity. Applied Catalysis A, General, 2018, 562: 114–119

[21] Jiang Z, Shen B X, Zhao J G, Wang L, Kong L T, Xiao W G. Enhancement of catalytic performances for the conversion of chloromethane to light olefins over SAPO-34 by modification with metal chloride. Industrial & Engineering Chemistry Research, 2015, 54(49): 12293–12302

[22] Nikolenko N V, Kozhevnikov I V, Kostyniuk A O, Bayahia H, Kalashnykov Y V. Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II) precursor. Journal of Saudi Chemical Society, 2018, 22: 372–379

[23] Ayoub G, Karadeniz B, Howarth A J, Farha O K, Đilović I, Germann L S, Dinnebier R E, Užarević K, Friščić T. Rational synthesis of mixed-metal microporous metal-mrganic frameworks with controlled composition using mechanochemistry. Chemistry of Materials, 2019, 31: 5494–5501

[24] Huang Y H, Lo W S, Kuo Y W, Chen W J, Lin C H, Shieh F. Green and rapid synthesis of zirconium metal-organic frameworks via mechanochemistry: UiO-66 analog nanocrystals obtained in one hundred seconds. Chemical Communications, 2017, 53: 5818–5821

[25] Zhan W C, Yang S Z, Zhang P F, Guo Y L, Lu G Z, Chisholm M F, Dai S. Incorporating rich mesoporosity into a ceria-based catalyst via mechanochemistry. Chemistry of Materials, 2017, 29: 7323–7329

[26] Szymański M P, Jędrzejewska H, Wierzbicki M, Szumna A. On the mechanism of mechanochemical molecular encapsulation in peptidic capsules. Physical Chemistry Chemical Physics, 2017, 19: 15676–15680

[27] Do J, Frisčic T. Mechanochemistry: a force of synthesis. ACS Central Science, 2017, 3: 13–19

[28] James S L, Adams C J, Bolm C, Braga D, Collier P, Friščić T, Grepioni F, Harris K D M, Hyett G, Jones W, . Mechanochemistry: opportunities for new and cleaner synthesis. Chemical Society Reviews, 2012, 41: 413–447

[29] Zhao J P, Shu Y, Zhang P F. Solid-state CTAB-assisted synthesis of mesoporous Fe₃O₄ and Au@Fe₃O₄ by mechanochemistry. Chinese Journal of Catalysis, 2019, 40: 1078–1084

[30] Shu Y, Chen H, Chen N Q, Duan X L, Zhang P F, Yang S Z, Bao Z H, Wu Z L, Dai S. A principle for highly active metal oxide catalysts via NaCl-based solid solution. Chem, 2020, 6: 1–19

[31] Bao J F, Chen H, Yang S Z, Zhang P F. Mechanochemical redox-based synthesis of highly porous Co_xMn_1−xO_y catalysts for total oxidation. Chinese Journal of Catalysis, 2020, 41: 1846–1854

[32] Kong L T, Zhang M, Liu X, Ma F Y, Wei B, Wumaier K, Zhao J G, Lu Z P, Sun J G, Chen J, . Green and rapid synthesis of iron molybdate catalyst by mechanochemistry and their catalytic performance for the oxidation of methanol to formaldehyde. Chemical Engineering Journal, 2019, 364: 390–400

[33] House M P, Carley A F, Echeverriavalda R, Bowker M. Effect of varying the cation ratio within iron molybdate catalysts for the selective oxidation of methanol. Journal of Physical Chemistry C, 2008, 112: 4333–4341

[34] Liardet L, Hu X. Amorphous cobalt vanadium oxide as a highly active electrocatalyst for oxygen evolution. ACS Catalysis, 2017, 8: 644–650

[35] Li X W, Sun Y J, Xiong T, Jiang G M, Zhang Y X, Wu Z B, Dong F. Activation of amorphous bismuth oxide via plasmonic Bi metal for efficient visible-light photocatalysis. Journal of Catalysis, 2017, 352: 102–112

[36] Yan Y, Xu H, Guo W, Huang Q L, Zheng M B, Pang H, Xue H G. Facile synthesis of amorphous aluminum vanadate hierarchical microspheres for supercapacitors. Inorganic Chemistry Frontiers, 2016, 3: 791–797

[37] Karelovic A, Ruiz P. The role of copper particle size in low pressure methanol synthesis via CO₂ hydrogenation over Cu/ZnO catalysts. Catalysis Science & Technology, 2015, 5: 869–881

[38] Qu Y Q, Yang H B, Yang N, Zhu H Y, Zou G T. The effect of reaction temperature on the particle size, structure and magnetic properties of coprecipitated CoFe₂O₄ nanoparticles. Materials Letters, 2006, 60: 3548–3552

[39] Bai X F, Wei J, Tian B B, Liu Y, Reiss T, Guiblin N, Gemeiner P, Dkhil B, Infante I C. Size effect on optical and photocatalytic properties in BiFeO₃ nanoparticles. Journal of Physical Chemistry C, 2016, 120: 3595–3601

[40] Zhang S, Zhang Y K, Hu R, Zhen B, Han M H. Surface structure and activity of iron molybdate catalyst for methanol oxidation to formaldehyde. CIESC Journal, 2016, 67(9): 3678–3683

[41] Xu Q, Jia G Q, Zhang J, Feng Z C, Li C. Surface phase composition of iron molybdate catalysts studied by UV Raman spectroscopy. Journal of Physical Chemistry C, 2008, 112: 9387–9393

[42] Li D, Xue J Q, Ma J, Tang J L. Synthesis of Fe₂(MoO₄)₃/MoO₃ heterostructured microrods and photocatalytic performances. New Journal of Chemistry, 2016, 40: 3330–3335

[43] Brookes C, Bowker M, Gibson E K, Gianolio D, Mohammed K M H, Parry S, Rogers S M, Silverwooda L P, Wells P P. In situ spectroscopic investigations of MoO_x/Fe₂O₃ catalysts for the selective oxidation of methanol. Catalysis Science & Technology, 2016, 6: 722–730

[44] Brookes C, Wells P P, Cibin G, Dimitratos N, Jones W, Morgan D J, Bowker M. Molybdenum oxide on Fe₂O₃ core-shell catalysts: probing the nature of the structural motifs responsible for methanol oxidation catalysis. ACS Catalysis, 2014, 4: 243–250

[45] Brookes C, Wells P P, Dimitratos N, Jones W, Gibson E K, Morgan D J, Cibin G, Nicklin C, Mora-Fonz D, Scanlon D O, . The nature of the molybdenum surface in iron molybdate. The active phase in selective methanol oxidation. Journal of Physical Chemistry C, 2014, 118: 26155–26161

[46] Bowker M, Brookes C, Carley A F, House M P, Kosif M, Sankar G, Wawata I, Wells P P, Yaseneva P. Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe₂O₃ surface doped with Mo oxide. Physical Chemistry Chemical Physics, 2013, 15: 12056–12067

[47] Chowdhry U, Ferretti A, Firment L E, Machiels C J, Ohuchi F, Sleight A W, Staley R H. Mechanism and surface structural effects in methanol oxidation over molybdates. Applied Surface Science, 1984, 19(1-4): 360–372

[48] Farneth W E, Ohuchi F, Staley R H, Chowdhry U, Sleight A W. Mechanism of partial oxidation of methanol over molybdenum(VI) oxide as studied by temperature-programmed desorption. Journal of Physical Chemistry, 1985, 89: 2493–2497

[49] Xie X W, Li Y, Liu Z Q, Haruta M, Shen W J. Low-temperature oxidation of CO catalysed by Co₃O₄ nanorods. Nature, 2009, 458: 746–749

[50] Lv C Q, Liu C, Wang G C. A DFT study of methanol oxidation on Co₃O₄. Catalysis Communications, 2014, 45: 83–90

[51] Seo C W, Jung K D, Lee K Y, Yoo K S. Influence of structure type of Al₂O₃ on dehydration of methanol for dimethyl ether synthesis. Industrial & Engineering Chemistry Research, 2008, 47: 6573–6578

[52] Akarmazyan S S, Panagiotopoulou P, Kambolis A, Papadopoulou C, Kondarides D I. Methanol dehydration to dimethylether over Al₂O₃ catalysts. Applied Catalysis B: Environmental, 2014, 14: 136–148

[53] Huang Y, Cong L Y, Yu J, Eloy P, Ruiz P. The surface evolution of a catalyst jointly influenced by thermal spreading and solid-state reaction: a case study with an Fe₂O₃-MoO₃ system. Journal of Molecular Catalysis A Chemical, 2009, 302: 48–53

[54] Thavornprasert K, Capron M, Jalowieckiduhamel L, Gardoll O, Trentesaux M, Mamede A, Fang G, Faye J, Touati N, Vezin H, . Highly productive iron molybdate mixed oxides and their relevant catalytic properties for direct synthesis of 1,1-dimethoxymethane from methanol. Applied Catalysis B: Environmental, 2014, 145: 126–135

[55] Wang C, Jia S Y, Zhang Y C, Nian Y, Wang Y, Han Y, Liu Y, Ren H T, Wu S H, Yao K X, . Catalytic reactivity of Co₃O₄ with different facets in the hydrogen abstraction of phenol by persulfate. Applied Catalysis B: Environmental, 2020, 270: 118819

[56] Zhang Q, Mo S P, Chen B X, Zhang W X, Huang C L, Yea D. Hierarchical Co₃O₄ nanostructures in-situ grown on 3D nickel foam towards toluene oxidation. Molecular Catalysis, 2018, 454: 12–20

[57] Wang K, Cao Y L, Hu J D, Li Y Z, Xie J, Jia D Z. Solvent-free chemical approach to synthesize various morphological Co₃O₄ for CO oxidation. ACS Applied Materials & Interfaces, 2017, 9: 16128–16137

[58] Zafeiratos S, Dintzer T, Teschner D, Blume R, Hävecker M, Knop-Gericke A, Schlögl R. Methanol oxidation over model cobalt catalysts: influence of the cobalt oxidation state on the reactivity. Journal of Catalysis, 2010, 269: 309–317

Acknowledgments

We thank the Natural Science Foundation Project of Xinjiang Uygur Autonomous (Grant No. 2019D01C084) for financial support. We thank the Xinjiang University Institute of Experimental Center for material characterization and analysis.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-2008-8 and is accessible for authorized users.

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