Sol–gel catalysts for synthetic organic chemistry: milestones in 30 years of successful innovation
Source abstract
Abstract
First commercialized in the second half of the 1990s as organosilica-entrapped lipases, sol-gel catalysts share several unique properties that make them ideally suited for process chemistry, namely synthetic organic chemistry in the fine chemicals industry. Is their application potential fully realized? What are the obstacles to their widespread uptake in the specialty and fine chemicals industry? Can they also be employed in visible-light photocatalysis? [Figure not available: see fulltext.]
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Mesoporous Materials and Catalysis · Enzyme Catalysis and Immobilization · Polyoxometalates: Synthesis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (68)
Show source-provided references
1. Braun S, Shtelzer S, Rappoport S, Avnir D, Ottolenghi M (1992) Biocatalysis by sol-gel entrapped enzymes. J Non-Cryst Solids 147–148:739–74310.1016/S0022-3093(05)80708-2 ↗
2. López T, Bosch P, Asomoza M, Gomez R (1992) Ru/SiO2-impregnated and sol-gel-prepared catalysts: synthesis, characterization, and catalytic properties. J Catal 133:247–25910.1016/0021-9517(92)90201-R ↗
3. Avnir D (1995) Organic chemistry within ceramic matrixes: doped sol-gel materials. Acc Chem Res 28:328–33410.1021/ar00056a002 ↗
4. Rosenfeld A, Avnir D, Blum J (1993) Sol-gel encapsulated transition metal quaternary ammonium ion pairs as highly efficient recyclable catalysts. J Chem Soc Chem Commun 583–584. https://pubs.rsc.org/en/content/articlelanding/1993/c3/c39930000583#!divAbstract10.1039/C39930000583 ↗
5. Cauqui MA, Rodríguez-Izquierdo JM (1992) Application of the sol-gel methods to catalyst preparation. J Non-Cryst Solids 147/148:724–73810.1016/S0022-3093(05)80707-0 ↗
6. Yanagisawa T, Shimizu T, Kuroda K, Kato C (1990) The preparation of alkyltrimethylammonium-kanemite complexes and their conversion to microporous materials. Bull Chem Soc Jpn 63:988–99210.1246/bcsj.63.988 ↗
7. Kröcher O, Köppel RA, Baiker A (1996) Sol–gel derived hybrid materials as heterogeneous catalysts for the synthesis of N,N-dimethylformamide from supercritical carbon dioxide. Chem Commun 1497–1498. https://pubs.rsc.org/en/content/articlelanding/1996/cc/cc9960001497#!divAbstract10.1039/CC9960001497 ↗
8. Reetz MT, Zonta A, Simpelkamp J (1995) Efficient heterogeneous biocatalysts by entrapment of lipases in hydrophobic sol–gel materials. Angew Chem Int Ed Engl 34:301–30310.1002/anie.199503011 ↗
9. Reetz MT, Zonta A, Simpelkamp J (1996) Efficient immobilization of lipases by entrapment in hydrophobic sol-gel materials. Biotechnol Bioeng 49:527–53410.1002/(SICI)1097-0290(19960305)49:5<527::AID-BIT5>3.0.CO;2-L ↗
10. Reetz MT, Tielmann P, Wiesenhöfer W, Könen W, Zonta A (2003) Second generation sol-gel encapsulated lipases: robust heterogeneous biocatalysts. Adv Synth Catal 345:717–72810.1002/adsc.200303016 ↗
11. Ciriminna R, Demma Carà P, Sciortino M, Pagliaro M (2011) Catalysis with doped sol-gel silicates. Adv Synth Catal 353:677–68710.1002/adsc.201000731 ↗
12. Avnir D, Blum J, Nairoukh Z (2015) Better catalysis with organically modified sol-gel materials. In: Levy D, Zayat M (eds) The sol-gel handbook, vol 2, Wiley-VCH, Weinheim, Germany, pp 963–98510.1002/9783527670819.ch31 ↗
13. Esposito S (2019) “Traditional” sol-gel chemistry as a powerful tool for the preparation of supported metal and metal oxide catalysts. Materials 12:66810.3390/ma12040668 ↗
14. Ozin G (1992) Nanochemistry: synthesis in diminishing dimensions. Adv Mater 4:612–64910.1002/adma.19920041003 ↗
15. Pagliaro M (2015) Advancing nanochemistry education. Chem Eur J 21:11931–1193610.1002/chem.201501042 ↗
16. Pagliaro M (2019) Chemistry education fostering creativity in the digital era. Isr J Chem 59:565–57110.1002/ijch.201800179 ↗
17. Hübner S, de Vries JG, Farina V (2016) Why does industry not use immobilized transition metal complexes as catalysts? Adv Synth Catal 358:3–2510.1002/adsc.201500846 ↗
18. Cole-Hamilton DJ (2003) Homogeneous catalysis–new approaches to catalyst separation, recovery, and recycling. Science 299:1702–170610.1126/science.1081881 ↗
19. Ciriminna R, Blum J, Avnir D, Pagliaro M (2000) Sol-gel entrapped TEMPO for the selective oxidation of methyl alfa-D-glucopyranoside. Chem Commun 1441–1442. https://pubs.rsc.org/en/content/articlelanding/2000/cc/b003096l#!divAbstract10.1039/b003096l ↗
20. Ciriminna R, Bolm C, Fey T, Pagliaro M (2002) Sol-gel ormosils doped with TEMPO as recyclable catalysts for the selective oxidation of alcohols. Adv Synth Catal 344:159–16310.1002/1615-4169(200202)344:2<159::AID-ADSC159>3.0.CO;2-Q ↗
21. Michaud A, Gingras G, Morin M, Béland F, Ciriminna R, Avnir D, Pagliaro M (2007) SiliaCat TEMPO: an effective and useful oxidizing catalyst. Org Process Res Dev 11:766–76810.1021/op700050j ↗
22. Pandarus V, Ciriminna R, Gingras G, Béland F, Drobod M, Jima O, Pagliaro M (2013) Greening heterogeneous catalysis for fine chemicals. Tetrahedron Lett 54:1129–113210.1016/j.tetlet.2012.12.058 ↗
23. Pagliaro M, Bolm C, Ciriminna R (2002) Sol-gel ormosils doped with TEMPO as recyclable catalysts for the selective oxidation of alcohols. Adv Synth Catal 344:159–16310.1002/1615-4169(200202)344:2<159::AID-ADSC159>3.0.CO;2-Q ↗
24. Fidalgo A, Ciriminna R, Ilharco LM, Pagliaro M (2005) Role of the alkyl-alkoxide precursor on the structure and catalytic properties of hybrid sol-gel catalysts. Chem Mater 17:6686–669410.1021/cm051954x ↗
25. Hughes N (2017) Development of sustainable catalytic systems for oxidation reactions. Ph.D. Thesis, Queen’s University Belfast. https://pure.qub.ac.uk/portal/en/theses/development-of-sustainable-catalytic-systems-for-oxidation-reactions(acf2d91f-e0ae-414d-b6ef-23da3c56e750).html
26. Jun SH, Park SG, Kang NG (2019) One-pot method of synthesizing TEMPO-oxidized bacterial cellulose nanofibers using immobilized TEMPO for skincare applications. Polymers 11:104410.3390/polym11061044 ↗
27. Saito T, Nishiyama Y, Putaux JL, Vignon M, Isogai A (2006) Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose. Biomacromolecul 7:1687–169110.1021/bm060154s ↗
28. Pagliaro M (2018) Cellulose nanofiber: an advanced biomaterial soon to become ubiquitous. Chim Oggi 36(4):61–62
29. Jetten J, Besemer A (2003) Process for the recovery of nitroxy compounds from organic solutions and oxidation process. US20050154206A1
30. Patankar C, Renneckar S (2017) Greener synthesis of nanofibrillated cellulose using magnetically separable TEMPO nanocatalyst. Green Chem 19:4792–479710.1039/C7GC02383A ↗
31. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–8510.1039/C0NR00583E ↗
32. Ferrer ML, del Monte F, Levy D (2002) A novel and simple alcohol-free sol−gel route for encapsulation of labile proteins. Chem Mater 14:3619–362110.1021/cm025562r ↗
33. Pagliaro M, Pandarus V, Béland F, Ciriminna R, Palmisano G, Demma Carà P (2011) A new class of heterogeneous Pd catalysts for synthetic organic chemistry. Catal Sci Technol 1:736–73910.1039/c1cy00119a ↗
34. Pandarus V, Ciriminna R, Béland F, Pagliaro M (2011) A new class of heterogeneous Pt catalysts for the chemoselective hydrogenation of nitroarenes. Adv Synth Catal 353:1306–131610.1002/adsc.201000945 ↗
35. Ciriminna R, Ilharco LM, Pandarus V, Fidalgo A, Béland F, Pagliaro M (2014) Towards waste free organic synthesis via nanostructured hybrid silicas. Nanoscale 6:6293–630010.1039/C3NR06127B ↗
36. Fidalgo A, Ciriminna R, Lopes L, Pandarus V, Béland F, Ilharco LM, Pagliaro M (2013) The sol-gel entrapment of noble metals in hybrid silicas: a molecular insight. Chem Centr J 7:16110.1186/1752-153X-7-161 ↗
37. Ciriminna R, Pandarus V, Béland F, Pagliaro M (2016) Fine chemical synthesis under flow using the siliacat catalysts. Catal Sci Technol 6:4678–468510.1039/C6CY00038J ↗
38. Ciriminna R, Pandarus V, Fidalgo A, Ilharco LM, Béland F, Pagliaro M (2015) SiliaCat: a versatile catalyst series for synthetic organic chemistry. Org Process Res Dev 19:755–76810.1021/acs.oprd.5b00137 ↗
39. Ciriminna R, Della Pina C, Falletta E, Teles JH, Pagliaro M (2016) Industrial applications of gold catalysis. Angew Chem Int Ed 55:14210–1421710.1002/anie.201604656 ↗
40. Ramirez Côté C, Ciriminna R, Pandarus V, Béland F, Pagliaro M (2018) Comparing the pyrophoricity of palladium catalysts for heterogeneous hydrogenation. Org Process Res Dev 22:1852–185510.1021/acs.oprd.8b00242 ↗
41. Ciriminna R, Pandarus V, Béland F, Pagliaro M (2014) Catalytic hydrogenation of squalene to squalane. Org Process Res Dev 18:1110–111510.1021/op5002337 ↗
42. Pandarus V, Ciriminna R, Kaliaguine S, Béland F, Pagliaro M (2015) Heterogeneously catalyzed hydrogenation of squalene to squalane under mild conditions. ChemCatChem 7:2071–207610.1002/cctc.201402668 ↗
43. Pandarus V, Ciriminna R, Kaliaguine S, Béland F, Pagliaro M (2017) Solvent-free chemoselective hydrogenation of squalene to squalane. ACS Omega 2:3989–399610.1021/acsomega.7b00625 ↗
44. Pagliaro M, Sciortino M, Ciriminna R, Alonzo G, De Schrijver A (2011) From molecules to systems: sol-gel microencapsulation in silica-based materials. Chem Rev 111:765–78910.1021/cr100161x ↗
45. Pandarus V, Ciriminna R, Gingras G, Béland F, Pagliaro M, Kaliaguine S (2019) Waste-free and efficient hydrosilylation of olefins. Green Chem 21:129–14010.1039/C8GC02569J ↗
46. Ghahremani M, Ciriminna R, Pandarus V, Scurria A, La Parola V, Giordano F, Avellone G, Béland F, Karimi B, Pagliaro M (2018) Green and direct synthesis of benzaldehyde and benzyl benzoate in one pot. ACS Sust Chem Eng 6:15441–1544610.1021/acssuschemeng.8b03893 ↗
47. Lemay M, Pandarus V, Simard M, Marion O, Tremblay L, Béland F (2010) SiliaCat S-Pd and SiliaCat DPP-Pd: highly reactive and reusable heterogeneous silica-based palladium catalysts. Top Catal 53:1059–106210.1007/s11244-010-9532-6 ↗
48. de Juan M. Muñoz, Alcázar J, de la Hoz A, Díaz-Ortiz A(2012) Cross‐coupling in flow using supported catalysts: mild, clean, efficient and sustainable Suzuki–Miyaura coupling in a single pass Adv Synth Catal 354:3456–346010.1002/adsc.201200678 ↗
49. Egle B, de Muñoz JM, Alonso N, De Borggraeve WM, de la Hoz A, Díaz-Ortiz A, Alcázar J (2014) First example of alkyl–aryl Negishi cross-coupling in flow: mild, efficient and clean introduction of functionalized alkyl groups. J Flow Chem 4:22–2510.1556/JFC-D-13-00009 ↗
50. Greco R, Goessler W, Cantillo D, Kappe CO (2015) Benchmarking immobilized di- and triarylphosphine palladium catalysts for continuous-flow cross-coupling reactions: efficiency, durability, and metal leaching studies. ACS Catal 5:1303–131210.1021/cs5020089 ↗
51. McAfee SM, Welch GC (2019) Development of organic dye‐based molecular materials for use in fullerene‐free organic solar cells. Chem Rec 19:989–100710.1002/tcr.201800114 ↗
52. Alltucker K (2019) Blood pressure drug recall: FDA investigates foreign plants that made drugs with cancer-causing impurities, USA Today, 17 December 2019. https://eu.usatoday.com/story/news/health/2019/01/14/fda-zhejiang-huahai-hetero-labs-blood-pressure-drug-recall-cancer/2547858002/
53. Pandarus V, Desplantier-Giscard D, Gingras G, Ciriminna R, Béland F, Pagliaro M (2013) Greening the valsartan synthesis: scale-up of key Suzuki-Miyaura coupling over SiliaCat DPP-Pd. Org Process Res Dev 17:1492–149710.1021/op400118f ↗
54. Martin AD, Siamaki AR, Belecki K, Gupton F (2015) A flow-based synthesis of telmisartan. J Flow Chem 5:145–14710.1556/JFC-D-15-00002 ↗
55. Ciriminna R, Hesemann P, Moreau J, Carraro M, Campestrini S, Pagliaro M (2006) Aerobic oxidation of alcohols in carbon dioxide with silica-supported ionic liquids doped with perruthenate. Chem Eur J 12:5220–522410.1002/chem.200501556 ↗
56. Ciriminna R, Campestrini S, Pagliaro M (2006) FluoRuGel: a versatile catalyst for aerobic alcohol oxidation in dense phase carbon dioxide. Org Biomol Chem 4:2637–264110.1039/b604663k ↗
57. Thomas S (2018) Leaders in performance and speciality chemicals. Chemspec Europe. www.chemspeceurope.com/2019/assets/CSE18_RSCArchive_2016_14.pdf
58. Ciriminna R, Pagliaro M (2013) Green chemistry in the fine chemicals and pharmaceutical industries. Org Process Res Dev 17:1479–148410.1021/op400258a ↗
59. Pagliaro M (2019) An industry in transition: the chemical industry and the megatrends driving its forthcoming transformation. Angew Chem Int Ed 58:11154–1115910.1002/anie.201905032 ↗
60. Ciriminna R, Pagliaro M, Luque R (2019) Heterogeneous catalysis under flow for the 21st century fine chemical industry, Preprints 2019010175. https://doi.org/10.20944/preprints201901.0175.v110.20944/preprints201901.0175.v1 ↗
61. Bryan MC, Dunn PJ, Entwistle D, Gallou F, Koenig SG, Hayler JD, Hickey MR, Hughes S, Kopach ME, Moine G, Richardson PI, Roschangar F, Steven A, Weiberth FJ (2018) Key green chemistry research areas from a pharmaceutical manufacturers’ perspective revisited. Green Chem 20:5082–510310.1039/C8GC01276H ↗
62. Jensen KF (2017) Flow chemistry-microreaction technology comes of age. AIChE J 63:858–86910.1002/aic.15642 ↗
63. Porcu L (2019) A flow chemistry approach for the supply risk management: optimization of industrial processes. Making Pharmaceuticals, Milano
64. Zhang Y, Ciriminna R, Palmisano G, Xu YJ, Pagliaro M (2014) Sol-gel entrapped visible light photocatalysts for selective conversions. RSC Adv 4:18341–1834610.1039/C4RA01031K ↗
65. Ciriminna R, Delisi R, Parrino F, Palmisano L, Pagliaro M (2017) Tuning the photocatalytic activity of bismuth wolframate: towards selective oxidations for the biorefinery driven by solar-light. Chem Commun 53:7521–752410.1039/C7CC04242F ↗
66. Ciriminna R, Delisi R, Xu YJ, Pagliaro M (2016) Towards the waste-free synthesis of fine chemicals with visible light. Org Process Res Dev 20:403–40810.1021/acs.oprd.5b00424 ↗
67. Smith JD, Jamhawi AM, Jasinski JB, Gallou F, Ge J, Advincula R, Liu J, Handa S (2019) Organopolymer with dual chromophores and fast charge-transfer properties for sustainable photocatalysis. Nat Commun 10:1837
68. Karimi B, Ghahremani M, Ciriminna R, Pagliaro M (2018) New stable catalytic electrodes functionalized with TEMPO for the waste-free oxidation of alcohols. Org Process Res Dev 22:1298–130510.1021/acs.oprd.8b00156 ↗