1、Harold H. KungChemical Engineering DepartmentNorthwestern UniversityEvanston, IL 60208-3120October 13, 2019What would one like to accomplish in total catalyst synthesis? Shape of the cavity Path to cavity Ability to design and position ancillary groups Complete atomic control of active site (metal,

2、oxide)Metal Crystallite Catalytic Active Phase Surface arrangement of atoms Composition Nature of support Location of crystallite on support (defect sites) Structure sensitivity Electronic effect Ligand effect Metal clusters derived from metal carbonyl complexesBC Gates J. Molec. Catal. A Chem 163 (

3、2000) 55Os5C on MgOIr4 in zeoliteSize-selective cluster beam deposition of Aun clusters on MgOHeiz, Sanchez, Abbet, Schneider, Chem. Phys. 262 (2000) 189.MS signal of C16O18O in TPD after exposure to 18O2 and then COAaron S. Eppler, Gnther Rupprechter, Lszl Guczi, and Gabor A. Somorjai, J. Phys. Che

4、m. B 101 (2019) 9973.Array of Pt on silicaDeposition of metal clusters using lithographyInsufficient control of shape, exact size, and atom locations; current limit on smallest size achieved.P-SO32- + Mn+(aq) P-SO32-Mn+P-SO32-Mn+ + NaBH4 P-SO32-/MoPreparation of uniform sized metal particles using f

5、unctional resinsCorain, Centomo, Ferrari Meyer-Zaika, Schmid, Gold2019, October 2019.Control of surface coordinative unsaturation sites of aluminum oxide (Al2O3) by synthesis Active sites are surface exposed Al ions (Lewis acid sites).AlOAlOOAlOOOActive siteAlOAlOOAlOOOHigh temp-H2OAlOHOHOO(HO)3Al(H

6、O)3AlnAlOHOHHOHOOHOHOAlAlOOO-H2OAlOAlOOAlOOOAlOAlOOAlOOAlOOAlOOOHigh temp-H2OAlOHOHOO(HO)3Al(HO)3AlAlAlOHOHOO(HO)3Al(HO)3AlnAlOHOHHOHOnAlOHOHHOHOAlAlOHOHHOHOOHOHOAlAlOOOOHOHOAlAlOOOAlAlOOO-H2O-H2OAlAlORORROROROORNRH2H2OOH2RNAlAlOOOH2RNStrategy: use amine (Lewis base) to preserve Lewis acidity.AlORNR

7、H2RORO2monomerCan make monomerAmine protection is retainedFinal solid an active catalystKozlov, Kung, Xue, and Kung, Angew. Chem. Int. Ed. 42(2019) 2415051015202530050010001500Time (min)Conversion of epoxide (%)Conversion of cyclopentene oxide in reaction with piperidine catalyzed by various alumina

8、s. PPD-Al2O3, SG-Al2O3-200, SG-Al2O3-500-H2O-200, SG-Al2O3-500-H2O, PA-Al2O3-500-H2O-200 PA-Al2O3-500-H2O, blank. O+HNOHNOH77oCO+HNOHNOHOHNOH77oCXue, Kung, Kozlov, Popp, and Kung, Catal. Today, 2019.Generation of active site by building on a well-defined structure001203cJ.M. Thomas, et al. Nature 39

9、8 (2019) 227; Angew. Chem. Int. Ed. 39 (2000) 2310.ReactantConv.1-ol1-ald 1-acid 1,6-acid 1,6-ol/al 2-ol/oneCoAlPO-18 (Co/P=0.04)C6H147.2%4.53.353.536.1CoAlPO-18 (Co/P=0.1)9.3%42.43331.61.924.5CoAlPO-36 (Co/P=0.04)5.2%8.73.810.229CoAlPO-34 (Co/P=0.1)7.9%7.36.229.419.73.930.91.5 MPa air, 373 K, 24 h,

10、 Selectivity %Hexane ( ) Oxidation Two Co(III) ions in CoAlPO-18 at the desired distance apart in Co/P = 0.1 samples. CoAlPO-36 of larger pore structure and shape, produces much more 3-ol and 3-one.Importance in controlling relative location of sitesRaja and Thomas, J. Molec. Catal. 181 (2019) 3-120

11、-100-80-60-40-200204060-120-100-80-60-40-200204060-120-100-80-60-40-200204060-120-100-80-60-40-200204060-120-100-80-60-40-20020406029Si NMR of (Si-O)n oligomer unitsAtom-by-Atom Synthesis of Metal-Oxygen ChainChang, Kung, and Kung, Chem. Comm. submittted. Metal-Oxygen Backbone of Designed Sequence a

12、nd StructureOSiMMolecular templating:A. Katz and M.E. Davis, Nature 403 (2000) 286. Introduce functional groups at specific locations in the cavity.Molecules diffuse through silica wall into and out of cavity.Preparing sites with predetermined spacingDufaud and Davis, JACS 125 (2019) 9403Table 3. Sy

13、nthesis of Bisphenol A with Sulfonic Acid Functionalized SBA-15 Silicas and para-Toluene Sulfonic Acida per site yield of bisphenol Abp, p/o, p molar ratiocatalystfunctional groupGCcNMRdGCcNMRd para-toluene sulfonic acid CH3aryl-SO3H 36 29 2 2.6 1-propane sulfonic acid CH3CH2CH2-SO3H 9.6e n.d.f 1.8e

14、 n.d. 11SBA Si-CH2CH2aryl-SO3H 13 11 3 3.0 9SBA Si-propyl-SO3H 8.8 8.4 10 6.4 10SBA Si-propyl-SO3H HO3S-propyl-Si 18 18 12 8.3Vronique Dufaud* and Mark E. Davis* , J. Am. Chem. Soc., 125 (31), 9403 -9413, 2019What would one like to accomplish in total catalyst synthesis? Shape of the cavity Path to

15、cavity Ability to design and position ancillary groups Complete atomic control of active siteEliminated pore diffusion control, Little shape selectivity. A. Corma, U. Diaz, M.E. Domine, V. Forns, Angew. Chem. Int. Ed. 39 (2000) 1499.(h00)K. Polborn and K. Severin, Chem. Commun. (2019) 2481-2482.Mole

16、cular ImprintingCat. 4 made from 2; control cat. 5 made from 1RPRPActive At restMolecular hinges to control accessibility of active sitesFigure 1 Molecular model of endoclucanase 12A and schematic model of the DMAAm-enzyme molecular switch. The red residues represent the catalytic glutamic acid side

17、 chains at the active site of EG 12A, the green residue is the Asn 55 position, the purple residue is the Ser 25 position, and the N-terminus is represented as the blue circle. Tsuyoshi Shimoboji, Edmund Larenas, Tim Fowler, Allan S. Hoffman,* and Patrick S. Stayton* Bioconjugate Chem., 14 (3), 517

18、-525, 2019Figure 4 Characterization of ONPC enzyme activities for free DMAAm-EG 12A conjugates in solution at as function of polymer size and conjugation site. The enzyme activities were measured for 100 nM conjugates using ONPC (8mM) as a substrate and normalized to the activity of N55C or S25C EG1

19、2A controls as 100% at each temperature. EG 12A-M10, 10 kDa DMAAm-EG12A conjugate; EG 12A-M6, 6 kDa DMAAm-EG 12A conjugate; EG 12A-M3, 3 kDa DMAAm-EG 12A conjugate; and EG 12A + M10, physical mixture of enzyme plus 10 kDa DMAAm. Tsuyoshi Shimoboji, Edmund Larenas, Tim Fowler, Allan S. Hoffman,* and

20、Patrick S. Stayton* Bioconjugate Chem., 14 (3), 517 -525, 2019Molecular Switching via RedoxReduction by ascorbic acidOxidation with ammonium persulfateConformational change monitored by circular dichroismS. Zahn and J.W. Canary, Angew. Chem. Int. Ed. 37 (2019) 305-V. Balzani, A. Credi, F.M. Raymo, J

21、.F. Stoddart, Angew. Chemie Int. Ed. 39 (2000)3348J. Rebek, Jr. Acc. Chem. Res. 17 (1984) 258V. Balzani, A. Credi, F.M. Raymo, J.F. Stoddart, Angew. Chemie Int. Ed. 39 (2000)3348pH-Driven translocation of Ni(II) ionAmendola, Fabbrizzi, Mangano, Pallavicini, Acc. Chem. Res. 34 (2019) 488.Translocatio

22、n of metal ion is signaled by quenching/revival of the emission of fluorescent probe (anthracene substituent)Mesoporous benzene-silicaS. Inagaki et al, Nature, 416 (2019) 304AlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlHRAlOOOOAlAlOOOOAlHRAlOOOOAlHRAlOOOOAlAlOOOOAlHR

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