Recent advances in the oxidation of cyclohexane catalyzed by metalloporphyrins

doi:10.16085/j.issn.1000-6613.2017-2249

Abstract

Abstract: Recent advances in catalytic oxidation of cyclohexane have been reviewed in detail,including the catalytic systems employing PhIO,PhI(OAc)₂,O₂,t-BuOOH,NaIO₄ and H₂O₂ as the oxidants. It is pointed out that the development of heterogeneous catalytic system employing O₂ as oxidant with high activity and selectivity will be the focus of oxidation of cyclohexane catalyzed by metalloporphyrin in the future,especially for the metalloporphyrin systems with multi metals. The metalloporphyrin with high catalytic performance both in activation of O₂ and in decomposition and transformation of cyclohexyl hydrogen peroxide through covalent bond to construct metalloporphyrin system with multi metals will increase the conversion of cyclohexane and the selectivity of oxidation product. This review can act as an important reference in the research and development of the catalytic system for the cyclohexane oxidation as well as other hydrocarbon oxidation and non-hydrocarbon oxidation.

Key words: alkane, metalloporphyrin, biomimetic catalysis, oxidation

摘要： 系统综述了金属卟啉催化氧化环己烷的最新研究进展，包括以PhIO、PhI （OAc）₂、O₂、t-BuOOH、NaIO₄和H₂O₂为氧化剂的各种氧化体系。认为开发以O₂为氧化剂、高活性高选择性的非均相金属卟啉催化体系是今后金属卟啉催化氧化环己烷的主要方向，尤其是多金属中心的金属卟啉体系，将对O₂具有高活化性能和对环己基过氧化氢分解转化具有高催化活性的金属卟啉共价键连组合，构筑多金属中心的金属卟啉体系，促进环己烷催化氧化体系中底物转化率和产物选择性的提高。本综述不仅对开发高活性、高选择性的环己烷催化氧化体系，改进目前工业上环己烷催化氧化体系具有重要的参考价值，而且对其他烃类C—H键和C—C键高效催化氧化体系，甚至其他氧化体系的研究开发也具有重要的参考价值。

关键词: 烷烃, 金属卟啉, 仿生催化, 氧化

CLC Number:

SHEN Haimin, WANG Yan, SHE Yuanbin. Recent advances in the oxidation of cyclohexane catalyzed by metalloporphyrins[J]. Chemical Industry and Engineering Progress, 2018, 37(06): 2031-2045.

沈海民, 王岩, 佘远斌. 金属卟啉催化氧化环己烷最新研究进展[J]. 化工进展, 2018, 37(06): 2031-2045.

References

[1] RANA S,JONNALAGADDA S B. CuO/Graphene oxide nanocomposite as highly active and durable catalyst for selective oxidation of cyclohexane[J]. Chemistry Select,2017,2(7):2277-2281.
[2] LIU X,CONTE M,HE Q,et al. Catalytic partial oxidation of cyclohexane by bimetallic Ag/Pd nanoparticles on magnesium oxide[J]. Chemistry A:European Journal,2017,23(49):11834-11842.
[3] KODERA M,ISHIGA S,TSUJI T,et al. Formation and high reactivity of the anti-dioxo form of high-spin Mu-oxodioxodiiron(Ⅳ) as the active species that cleaves strong C-H bonds[J]. Chemistry A:European Journal,2016,22(17):5924-5936.
[4] ALSHAMMARI A,KALEVARU V N,MARTINS A. Bimetallic catalysts containing gold and palladium for environmentally important reactions[J]. Catalysts,2016,6(97):1-24.
[5] LOPEZ-AUSENS T,BORONAT M,CONCEPCION P,et al. A heterogeneous mechanism for the catalytic decomposition of hydroperoxides and oxidation of alkanes over CeO₂ nanoparticles:a combined theoretical and experimental study[J]. Journal of Catalysis,2016,344:334-345.
[6] LU H Y,REN W Z,LIU P F,et al. One-step aerobic oxidation of cyclohexane to adipic acid using an Anderson-type catalyst[(C₁₈H₃₇)₂N(CH₃)₂]₆Mo₇O₂₄[J]. Applied Catalysis A:General,2012,441:136-141.
[7] XIAO Z,ZHAN W C,GUO Y,et al. The synthesis of Co-doped SAPO-5 molecular sieve and its performance in the oxidation of cyclohexane with molecular oxygen[J]. Chinese Journal of Catalysis,2016,37(2):273-280.
[8] FARHA O K,SHULTZ A M,SARJEANT A A,et al. Active-site-accessible, porphyrinic metal-organic framework materials[J]. Journal of the American Chemical Society,2011,133(15):5652-5655.
[9] YU H,PENG F,TAN J,et al. Selective catalysis of the aerobic oxidation of cyclohexane in the liquid phase by carbon nanotubes[J]. Angewandte Chemie-International Edition,2011,50(17):3978-3982.
[10] VAN DIJK V H A,SIMMELINK G,MUL G. The influence of water vapour on the photocatalytic oxidation of cyclohexane in an internally illuminated monolith reactor[J]. Applied Catalysis A:General,2014,470:63-71.
[11] YUAN Y,JI H B,CHEN Y X,et al. Oxidation of cyclohexane to adipic acid using Fe-porphyrin as a biomimetic catalyst[J]. Organic Process Research & Development,2004,8(3):418-420.
[12] CHEN Y,SHE Y,XU J,et al. Studies on QSAR of metalloporphyrin catalysts in the oxidation of cyclohexane to adipic acid[J]. Frontiers of Chemical Engineering in China,2007,1(2):155-161.
[13] LI H,SHE Y,WANG T. Advances and perspectives in catalysts for liquid-phase oxidation of cyclohexane[J]. Frontiers of Chemical Science and Engineering,2012,6(3):356-368.
[14] WANG T,SHE Y B,FU H Y,et al. Selective cyclohexane oxidation catalyzed by manganese porphyrins and co-catalysts[J]. Catalysis Today,2016,264:85-190.
[15] LI H,SHE Y B,FU H Y,et al. Synergistic effect of co-reactant promotes one-step oxidation of cyclohexane into adipic acid catalyzed by manganese porphyrins[J]. Canadian Journal of Chemistry,2015,93(7):696-701.
[16] SILVA G F,DA SILVA D C,GUIMARAES A S,et al. Cyclohexane hydroxylation by iodosylbenzene and iodobenzene,diacetate catalyzed by a new beta-octahalogenated Mn-porphyrin complex:the effect of meso-3-pyridyl substituents[J]. Journal of Molecular Catalysis A:Chemical,2007,266(1/2):274-283.
[17] HAO J M,CHENG H Y,WANG H J,et al. Oxidation of cyclohexane-a significant impact of stainless steel reactor wall[J]. Journal of Molecular Catalysis A:Chemical,2007,271(1/2):42-45.
[18] FENG D W,JIANG H L,CHEN Y P,et al. Metal-organic frameworks based on previously unknown Zr-8/Hf-8 cubic clusters[J]. Inorganic Chemistry,2013,52(21):12661-12667.
[19] MOGHADAM M,MIRKHANI V,TANGESTANINEJAD S,et al. Silica supported Mn(Br₈TPP)Cl and Mn(TPP)Cl as efficient and reusable catalysts for selective hydrocarbon oxidation under various reaction conditions:the effect of substituted bromines on the catalytic activity and reusability[J]. Journal of Molecular Catalysis A:Chemical,2008,288(1/2):116-124.
[20] FARZANEH F,POORKHOSRAVANI M,GHANDI M. Utilization of immobilized biomimetic iron complexes within nanoreactors of Al-MCM-41 as cyclohexane oxidation catalyst[J]. Journal of Molecular Catalysis A:Chemical,2009,308(1/2):108-113.
[21] DA SILVA D C,DEFREITAS-SILVA G,DO NASCIMENTO E,et al. Spectral, electrochemical, and catalytic properties of a homologous series of manganese porphyrins as cytochrome P450 model:the effect of the degree of beta-bromination[J]. Journal of Inorganic Biochemistry,2008,102(10):1932-1941.
[22] LEMOS B R S,CARVALHODA-SILVA D,MUSSI D Z,et al. High selectivity toward cyclohexanol in oxidation of cyclohexane using manganese aminophenylporphyrins as catalysts[J]. Applied Catalysis A:General,2011,400(1/2):111-116.
[23] DA SILVA V S,TEIXEIRA L I,DO NASCIMENTO E,et al. New manganese porphyrin as biomimetic catalyst of cyclohexane oxidation:effect of water or imidazole as additives[J]. Applied Catalysis A:General,2014,469:124-131.
[24] DA SILVA V S,IDEMORI Y M,DEFREITAS-SILVA G. Biomimetic alkane oxidation by iodosylbenzene and iodobenzene diacetate catalyzed by a new manganese porphyrin:water effect[J]. Applied Catalysis A:General,2015,498:54-62.
[25] CASTRO K A D F,BAIL A,GROSZEWICZ P B,et al. New oxidation catalysts based on iron(Ⅲ) porphyrins immobilized on Mg-Al layered double hydroxides modified with triethanolamine[J]. Applied Catalysis A:General,2010,386(1/2):51-59.
[26] UCOSKI G M,CASTRO K A D D,CIUFFI K J,et al. Use of iron and manganese porphyrins in solution and immobilized on silica obtained by the sol-gel process as catalyst in the oxidation of organic substrates[J]. Applied Catalysis A:General,2011,404(1/2):120-128.
[27] FERREIRA G K B,CASTRO K A D D,MACHADO G S,et al. Manganese porphyrin in solution and heterogenized in different materials mediates oxidation of hydrocarbons by iodosylbenzene[J]. Journal of Molecular Catalysis A:Chemical,2013,378:263-272.
[28] CASTRO K A D D,WYPYCH F,ANTONANGELO A,et al. Selective oxidation catalysts obtained by immobilization of iron(Ⅲ) porphyrins on thiosalicylic acid-modified Mg-Al layered double hydroxides[J]. Journal of Colloid and Interface Science,2016,478:374-383.
[29] LIU C X,LIU Q A,GUO C C,et al. Preparation and characterization of novel magnetic nanocomposite-bonded metalloporphyrins as biomimetic nanocatalysts[J]. Journal of Porphyrins and Phthalocyanines,2010,14(9):825-831.
[30] BOLZON L B,AIROLDI H R,ZANARDI F B,et al. Metalloporphyrin-functionalized hexagonal mesoporous silica:synthesis, structural properties and catalytic activity as cytochrome P450 model[J]. Microporous and Mesoporous Materials,2013,168:37-45.
[31] ZANATTA L D,BARBOSA I A,ZANARDI F B,et al. Hydrocarbon oxidation by iron-porphyrin immobilized on SBA-15 as biomimetic catalyst:role of silica surface[J]. RSC Advances,2016,6(106):104886-104896.
[32] MACHADO G S,CASTRO K A D F,DE LIMA O J,et al. Aluminosilicate obtained by sol-gel process as support for an anionic iron porphyrin:development of a selective and reusable catalyst for oxidation reactions[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2009,349(1-3):162-169.
[33] MACHADO G S,ARIZAGA G G C,WYPYCH F,et al. Immobilization of anionic metalloporphyrins on zinc hydroxide nitrate and study of an unusual catalytic activity[J]. Journal of Catalysis,2010,274(2):130-141.
[34] MACHADO G S,WYPYCH F,NAKAGAKI S. Anionic iron(Ⅲ) porphyrins immobilized on zinc hydroxide chloride as catalysts for heterogeneous oxidation reactions[J]. Applied Catalysis A:General,2012,413:94-102.
[35] MACHADO G S, GROSZEWICZ P B,CASTRO K A D D,et al. Catalysts for heterogeneous oxidation reaction based on metalloporphyrins immobilized on kaolinite modified with triethanolamine[J]. Journal of Colloid and Interface Science,2012,374:278-286.
[36] MACHADO G S,DE LIMA O J,CIUFFI K J,et al. Iron(Ⅲ) porphyrin supported on metahalloysite:an efficient and reusable catalyst for oxidation reactions[J]. Catalysis Science & Technology,2013,3(4):1094-1101.
[37] UCOSKI G M,NUNES F S,DEFREITAS-SILVA G,et al. Metalloporphyrins immobilized on silica-coated Fe₃O₄ nanoparticles:magnetically recoverable catalysts for the oxidation of organic substrates[J]. Applied Catalysis A:General,2013,459:121-130.
[38] ZOU C,ZHANG T F,XIE M H,et al. Four metalloporphyrinic frameworks as heterogeneous catalysts for selective oxidation and Aldol reaction[J]. Inorganic Chemistry,2013,52(7):3620-3626.
[39] XIE M H,YANG X L,HE Y B,et al. Highly efficient C-H oxidative activation by a porous Mn-Ⅲ-porphyrin metal-organic framework under mild conditions[J]. Chemistry A:European Journal,2013,19(42):14316-14321.
[40] BAGCHI V, BANDYOPADHYAY D. The porphyrin complex catalyzed dioxygen activation in presence of solid inorganic phosphates and small quantities of t-BuOOH[J]. Polyhedron,2008,27(5):1387-1392.
[41] MA D S,HU B H,LU C X. Selective aerobic oxidation of cyclohexane catalyzed by metallodeuteroporphyrin-IX-dimethylester[J]. Catalysis Communications,2009,10(6):781-783.
[42] XIE Y J,ZHANG F Y,LIU P L,et al. Synthesis and catalytic properties of trans-A₂B₂-type metalloporphyrins in cyclohexane oxidation[J]. Canadian Journal of Chemistry-Revue Canadienne De Chimie,2014,92(1):49-53.
[43] TABOR E,POLTOWICZ J,PAMIN K,et al. Influence of substituents in meso-aryl groups of iron μ-oxo porphyrins on their catalytic activity in the oxidation of cycloalkanes[J]. Polyhedron,2016,119:342-349.
[44] HU B C,ZHOU W Y,MA D S,et al. Metallo-deuteroporphyrins as catalysts for the oxidation of cyclohexane with air in the absence of additives and solvents[J]. Catalysis Communications,2008,10(1):83-85.
[45] ZHOU W Y,HU B C,LIU Z L. Metallo-deuteroporphyrin complexes derived from heme:a homogeneous catalyst for cyclohexane oxidation[J]. Applied Catalysis A:General,2009,358(2):136-140.
[46] SUN C G,HU B C,ZHOU W Y,et al. Synthesis of disulfide-derivatised metallodeuteroporphyrins as novel catalysts to imitate cytochrome P-450 in the selective oxidation of cyclohexane[J]. Journal of Chemical Research,2011(12):681-685.
[47] HUANG G,LIU S Y,WANG A P,et al.Catalysis of structure-like macromolecules supported manganese tetraphenylporphyrin for cyclohexane oxidation[J]. Catalysis Communications,2007,8:1183-1186.
[48] FU B,YU H C,HUANG J W,et al. Mn(Ⅲ) porphyrins immobilized on magnetic polymer nanospheres as biomimetic catalysts hydroxylating cyclohexane with molecular oxygen[J]. Journal of Molecular Catalysis A:Chemical,2009,298(1/2):74-80.
[49] HUANG G,LUO Z C,HU Y D,et al. Preparation and characterization of iron tetra(pentaflurophenyl)-porphyrin(TPFPP Fe) supported on boehmite(BM)[J]. Chemical Engineering Journal,2012,195:165-172.
[50] HUANG G,LIU Y,CAI J L,et al. Heterogeneous biomimetic catalysis using iron porphyrin for cyclohexane oxidation promoted by chitosan[J]. Applied Surface Science,2017,402:436-443.
[51] HUANG G,WANG W L,NING X X,et al. Interesting green catalysis of cyclohexane oxidation over metal tetrakis(4-carboxyphenyl) porphyrins promoted by zinc sulfide[J]. Industrial & Engineering Chemistry Research,2016,55(11):2959-2969.
[52] GUO X,SHEN D H,LI Y Y,et al. Immobilization of metalloporphyrin on organosilicon microsphere mixed with ceria as a new catalyst for oxidation of cyclohexane[J]. Journal of Molecular Catalysis A:Chemical,2011,351:174-178.
[53] XIE Y J,ZHANG F Y,LIU P L,et al. Catalytic oxidation of cyclohexane with dioxygen over boehmite supported trans-A₂B₂ type metalloporphyrins catalyst[J]. Journal of Molecular Catalysis A:Chemical,2014,386:95-100.
[54] GAO B J,CHEN Y J,LEI Q J. Hydroxylation of cyclohexane with molecular oxygen catalyzed by highly efficient heterogeneous Mn(Ⅲ) porphyrin catalysts prepared by special synthesis and immobilization method[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry,2012,74(1/2/3/4):455-465.
[55] GAO B J,QIAO Z W,SHI N. Preparation of heterogeneous cationic metalloporphyrin/heteropolyanion composite catalysts and their high catalytic activity in hydroxylation of cyclohexane with molecular oxygen[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry,2014,79(1/2):247-258.
[56] CAI J H,HUANG J W,YU H C,et al. Manganeseporphyrins immobilized on silica microspheres as biomimetic catalysts hydroxylating cyclohexane with molecular oxygen[J]. Journal of Sol-Gel Science and Technology,2011,58(3):698-704.
[57] JIANG Y X,SU T M,QIN Z Z,et al. A zinc sulfide-supported iron tetrakis(4-carboxyl phenyl) porphyrin catalyst for aerobic oxidation of cyclohexane[J]. RSC Advances,2015,5(31):24788-24794.
[58] HUANG G,GUO C C,TANG S S. Catalysis of cyclohexane oxidation with air using various chitosan-supported metallotetraphenylporphyrin complexes[J]. Journal of Molecular Catalysis A:Chemical,2007,261(1):125-130.
[59] HUANG G,LIU S Y,GUO Y A,et al. Immobilization of manganese tetraphenylporphyrin on boehmite and its catalysis for aerobic oxidation of cyclohexane[J]. Applied Catalysis A:General,2009,358(2):173-179.
[60] HUANG G,LI T M,LIU S Y,et al. A robust boehmite-supported cobalt tetraphenylporphyrin catalyst for aerobic oxidation of cyclohexane[J]. Applied Catalysis A:General,2009,371(1/2):161-165.
[61] SUN C G,HU B C,ZHAO D H,et al. Covalently immobilized Mn(Ⅲ) deuteroporphyrin on chitosan:an efficient and recyclable catalyst for aerobic oxidation of cyclohexane[J]. Journal of Applied Polymer Science,2012,125:E79-E87.
[62] ZHOU W Y,TIAN P,CHEN Y,et al. Effect of L-cysteine on the oxidation of cyclohexane catalyzed by manganeseporphyrin[J]. Bioorganic & Medicinal Chemistry Letters,2015,25(11):2356-2359.
[63] KUDRIK E V,ALBRIEUX F,AFANASIEV P,et al. μ-Nitrido diiron octaethylporphyrin complex:synthesis and properties[J]. Journal of Porphyrins and Phthalocyanines,2013,17(8/9):791-798.
[64] SINGH M K,BANDYOPADHYAY D. Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity[J]. Proceedings of the Indian Academy of Sciences-Chemical Sciences,2016,128(1):1-8.
[65] ZADEHAHMADI F,TANGESTANINEJAD S,MOGHADAM M,et al. Manganese(Ⅲ) tetrapyridylporphyrin-chloromethylated MIL-101 hybrid material:a highly active catalyst for oxidation of hydrocarbons[J]. Applied Catalysis A:General,2014,477:34-41.
[66] CASTRO K A D F,DE LIMA F H C,SIMOES M M Q,et al. Synthesis, characterization and catalytic activity under homogeneous conditions of ethylene glycol substituted porphyrin manganese(Ⅲ) complexes[J]. Inorganica Chimica Acta,2017,455:575-583.