Abstract
Herein, the metalloporphyrins Co(II) (5, 10, 15, 20-tetra (4-(3-(N-ethyl-4-pyridyl)pyrazolyl)phenyl)porphyrin) (CoTEtPyP) and Mn(III) (5, 10, 15, 20-tetra(4-(3-(N-ethyl-4-pyridyl)pyrazolyl)phenyl)porphyrin) (MnTEtPyP(OAc)) were synthesized and characterized spectroscopically. The cationic metalloporphyrins were firstly immobilized on the surface of SiO2 by electrostatic attractions with hydrothermal method to get the gels. Then, the gels were extracted by supercritical CO2 to remove the redundant solvent molecules and the unreacted metal salt. The structures and properties of porphyrin–SiO2 porous composites (PSC1 and PSC2) were characterized by Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, scanning electron microscopy, transmission electron microscope, powder X-ray diffraction, thermalgravimetric analysis and nitrogen sorption measurements. N2 absorptions have verified that the porous materials have large BET surface area and big N2 uptake capacity. The composites also have shown higher specific surface area and superior thermal stability. The catalytic activities of the new PSCs to the ethylbenzene oxidation carried out indicated that both of them exhibit highly selectivity of acetophenone (> 99%) with the conversion of 87.6% (PSC1) and 93.0% (PSC2), respectively.
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Wang RX, Gao JB, Jiao WZ (2009) A novel method for immobilization of Co tetraphenylporphyrins on P(4VP-co-St)/SiO2: efficient catalysts for aerobic oxidation of ethylbenzenes. Appl Surf Sci 255:4109–4113
Suslick KS, Bhyrappa P, Chou JH, Kosal ME, Nakagaky S, Smithenry DW, Wilson SR (2005) Microporous porphyrin solids. Acc Chem Res 38:283–291
Farha OK, Shultz AM, Sarjeant AA, Nguyen ST, Hupp JT (2011) Active-site-accessible, porphyrinic metal-organic framework materials. J Am Chem Soc 133:5652–5655
Fateeva A, Devautour-Vinot S, Heymans N, Devic T, Grenéche J, Wuttke S, Miller S, Lago A et al (2011) Series of porous 3-D coordination polymers based on iron(III) and porphyrin derivatives. Chem Mater 23:4641–4651
Fagadar-Cosma E, Mirica MC, Balcu I, Bucovicean C, Cretu C, Armeanu I, Fagadar-Cosma G (2009) Syntheses, spectroscopic and AFM characterization of some manganese porphyrins and their hybrid silica nanomaterials. Molecules 14:1370–1388
Shultz AM, Farha OK, Hupp JT, Nguyen ST (2011) Synthesis of catalytically active porous organic polymers from metalloporphyrin building blocks. Chem Sci 2:686–689
Alkordi MH, Liu Y, Larsen RW, Eubank JF, Eddaoudi M (2008) Zeolite-like metal-organic frameworks as platforms for applications: on metalloporphyrin-based catalysts. J Am Chem Soc 130:12639–12641
Fidalgo-Marijuan A, Barandika G, Bazán B, Urtiaga MK, Arriortua MI (2011) Self-assembly of iron TCPP (meso-tetra(4-carboxyphenyl)porphyrin) into a chiral 2D coordination polymer. Polyhedron 30:2711–2716
Guo CC, Song JX, Chen XB, Jiang GF (2000) A new evidence of the high-valent oxo–metal radical cation intermediate and hydrogen radical abstract mechanism in hydrocarbon hydroxylation catalyzed by metalloporphyrins. J Mol Catal A Chem 157:31–40
Fu L, Chen Y, Liu Z (2015) Cobalt catalysts embedded in N-doped carbon derived from cobalt porphyrin via a one-pot method for ethylbenzene oxidation. J Mol Catal A Chem 408:91–97
Gust D, Moore TA, Moore AL (2001) Mimicking photosynthetic solar energy transduction. Acc Chem Res 34:40–48
Cardoso WS, Francisco MSP, Landers R, Gushikem Y (2005) Co (II) porphyrin absorbed on SiO2/SnO2/phosphate prepared by the sol-gel method application in electroreduction of dissolved dioxygen. Electrochim Acta 50:4378–4384
Krishnakumar B, Balakrishna A, Nawabjan SA, Pandiyan V, Aguiar A, Sobral AJFN (2017) Solar and visible active amino porphyrin/ZnO for the degradation of naphthol blue black. J Phys Chem Solid 111:364–371
Yoshida A, Kakegawa N, Ogawa M (2003) Adsorption of a cationic porphyrin onto mesoporous silicas. Res Chem Intermed 29:721–731
Fujiwara ST, Gushikem Y, Pessoa CA, Nakagaki S (2005) Electrochemical studies of a new iron porphyrin entrapped in a propylpyridiniumsilsesquioxane polymer immobilized on a SiO2/Al2O3 surface. Electroanalysis 17:783–788
Kim JY, Lee KY, Kim S, Lee SJ (2015) Preparation of Mn(III)-porphyrin-immobilized Fe3O4@SiO2 mesoparticles and their use in heterogeneous catalysis of styrene epoxidation. Bull Korean Chem Soc 36:1936–1939
Pessôa CA, Gushikem Y, Nakagakib S (2002) Cobalt porphyrin immobilized on a niobium (V) oxide grafted-silica gel surface: study of the catalytic oxidation of hydrazine. Electroanalysis 14:1072–1076
Ryu S, Liu L, Berciaud S, Yu Y, Liu H, Kim P, Flynn GW, Brus LE (2010) Atmospheric oxygen binding and hole doping in deformed graphene on a SiO2 substrate. Nano Lett 10:4944–4951
Hofrichter J, Szafranek BN, Otto M, Echtermeyer TJ, Baus M, Majerus A, Geringer V, Ramsteiner M, Kurz H (2010) Synthesis of graphene on silicon dioxide by a solid carbon source. Nano Lett 10:36–42
Whittaker JD, Minot ED, Tanenbaum DM, McEuen PL, Davis RC (2006) Measurement of the adhesion force between carbon nanotubes and a silicon dioxide substrate. Nano Lett 5:953–957
Scherwitzl B, Lukesch W, Hirzer A, Albering J, Leising G, Resel R, Winkler A (2013) Initial steps of rubicene film growth on silicon dioxide. J Phys Chem C 117:4115–4123
Zhang Z, Li J, Yao Y, Sun S (2015) Permanently porous Co(II) porphyrin-based hydrogen bonded framework for gas adsorption and catalysis. Cryst Growth Des 15:5028–5033
Kishida T, Fujita N, Sada K, Shinkai S (2005) Porphyrin gels reinforced by sol-gel reaction via the organogel phase. Langmuir 21:9432–9439
Wang Z, Yuan S, Mason A, Reprogle B, Liu D, Yu L (2012) Nanoporous porphyrin polymers for gas storage and separation. Macromolecules 45:7413–7419
Modak A, Nandi M, Mondal J, Bhaumik A (2012) Porphyrin based porous organic polymers: novel synthetic strategy and exceptionally high CO2 adsorption capacity. Chem Commun 48:248–250
Takeuchi M, Tanaka S, Shinkai S (2005) On the influence of porphyrin p–p stacking on supramolecular chirality created in the porphyrin-based twisted tape structure. Chem Commun 44:5539–5541
Ahrenholtz SR, Epley CC, Morris AJ (2014) Solvothermal preparation of an electrocatalytic metalloporphyrin MOF thin film and its redox hopping charge-transfer mechanism. J Am Chem Soc 136:2464–2472
Wang Z, Lybarger LE, Wang W, Medforth CJ, Miller JE, Shelnutt JA (2008) Monodisperse porphyrin nanospheres synthesized by coordination polymerization. Nanotechnology 19:395604
Luca GD, Romeo A, Villari V, Micali N, Foltran I, Foresti I, Lesci IG, Roveri N, Zuccheri T, Scolaro LM (2009) Self-organizing functional materials via ionic self-assembly: porphyrins hand J-aggregates on synthetic chrysotile nanotubes. J Am Chem Soc 131:6920–6921
Valicsek Z, Horváth O (2013) Application of the electronic spectra of porphyrins for analytical purposes: the effects of metal ions and structural distortions. Microchem J 107:47–62
Rosenthal RA, Huffman KD, Fisette LW, Damphousse CW, Callaway WB, Malfroy B, Doctrow SR (2009) Orally available Mn porphyrins with superoxide dismutase and catalase activities. J Biol Inorg Chem 14:979–991
Yoo J, Park N, Park JH, Park JH, Kang S, Lee SM, Kim HJ, Jo H, Park J, Son SU (2015) Magnetically separable microporous Fe–porphyrin networks for catalytic carbene insertion into N–H bonds. ACS Catal 5:350–355
Farha OK, Malliakas CD, Kanatzidis MG, Hupp JT (2010) Control over catenation in metal-organic frameworks via rational design of the organic building block. J Am Chem Soc 132:950–952
Zhao X, Yuan L, Zhang Z, Wang Y, Yu Q, Li J (2016) Synthetic methodology for the fabrication of porous porphyrin materials with metal-organic-polymer Aerogels. Inorg Chem 55:5287–5296
Groen JC, Peffer LAA, pérez-Ramírez J (2003) Pore size determination in modified micro-and mesoporous materials. pitfalls and limitations in gas adsorption data analysis. Microporous Mesoporous Mater 60:1–17
Ohmura T, Usuki A, Fukumori K, Ohta T, Ito M, Tatsumi K (2006) New porphyrin-based metal-organic framework with high porosity: 2-D infinite 22.2-Å square-grid coordination network. Inorg Chem 45:7988–7990
Zhang JL, Huang JS, Che CM (2006) Oxidation chemistry of poly(ethylene glycol)-supported carbonylruthenium(ii) and dioxoruthenium(vi) meso-tetrakis(pentafluorophenyl)porphyrin. Chem Eur J 12:3020–3031
Meunier B (2000) In biomimetic oxidations catalyzed by transition metal complexes. Imperial College Press, London
Imran G, Pachamuthu MP, Maheswari R, Ramanathan A, Sardhar Basha SJ (2012) Catalytic activity of MnTUD-1 for liquid phase oxidation of ethylbenzene with tert-butyl hydroperoxide. J Porous Mater 19:677–682
Ricca C, Labat F, Russo N, Adamo C, Sicilia E (2014) Oxidation of ethylbenzene to acetophenone with N-doped graphene: insight from theory. J Phys Chem C 118:12275–12284
Gutmann B, Elsner P, Roberge D, Kappe CO (2013) Homogeneous liquid-phase oxidation of ethylbenzene to acetophenone in continuous flow mode. ACS Catal 3:2669–2676
Qiu Y, Yang C, Huo J, Liu Z (2016) Synthesis of Co-N-C immobilized on carbon nanotubes for ethylbenzene oxidation. J Mol Catal A Chem 424:276–282
Jiang W, Yang J, Liu YY, Ma JF (2016) Porphyrin-based mixed-valent Ag(I)/Ag(II) and Cu(I)/Cu(II) networks as efficient heterogeneous catalysts for the azide–alkyne ‘‘click’’ reaction and promising oxidation of ethylbenzene. Chem Commun 52:1373–1376
DeVos DE, Sels BF, Jacobs PA (2001) Immobilization of homogeneous oxidation catalysts. Adv Catal 46:1–87
Zou C, Zhang Z, Xu X, Gong Q, Li J, Wu CD (2011) A multifunctional organic–inorganic hybrid structure based on MnIII-porphyrin and polyoxometalate as a highly effective dye scavenger and heterogenous catalyst. J Am Chem Soc 134:87–90
Acknowledgements
The authors gratefully acknowledge the National Natural Science Foundation of China [Grant Numbers 21671158, 21271148 and 21773184] for the financial support of this work.
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Zhao, D., Wang, Y., Xu, Y. et al. Preparation, characterization and catalytic oxidation properties of silica composites immobilized with cationic metalloporphyrins. J Mater Sci 53, 14241–14249 (2018). https://doi.org/10.1007/s10853-018-2662-0
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DOI: https://doi.org/10.1007/s10853-018-2662-0