Complex organic molecules are of great importance to research and industrial chemistry and typically synthesized from smaller building blocks by multistep reactions. The ability to perform multiple (distinct) transformations in a single reactor would greatly reduce the number of manipulations required for chemical manufacturing, and hence the development of multifunctional catalysts for such one-pot reactions is highly desirable. Here we report the synthesis of a hierarchically porous framework, in which the macropores are selectively functionalized with a sulfated zirconia solid acid coating, while the mesopores are selectively functionalized with MgO solid base nanoparticles. Active site compartmentalization and substrate channelling protects base-catalysed triacylglyceride transesterification from poisoning by free fatty acid impurities (even at 50 mol%), and promotes the efficient two-step cascade deacetalization-Knoevenagel condensation of dimethyl acetals to cyanoates.
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The data that support the findings of this study are available from the corresponding author upon reasonable request.
Climent, M. J., Corma, A. & Iborra, S. Heterogeneous catalysts for the one-pot synthesis of chemicals and fine chemicals. Chem. Rev. 111, 1072–1133 (2010).
Climent, M. J., Corma, A. & Iborra, S. Homogeneous and heterogeneous catalysts for multicomponent reactions. RSC Adv. 2, 16–58 (2012).
Kulkarni, M. G. & Dalai, A. K. Waste cooking oil—an economical source for biodiesel: a review. Ind. Eng. Chem. Res. 45, 2901–2913 (2006).
Biju, A. T., Wurz, N. E. & Glorius, F. N-Heterocyclic carbene-catalyzed cascade reaction involving the hydroacylation of unactivated alkynes. J. Am. Chem. Soc. 132, 5970–5971 (2010).
Enders, D., Huettl, M. R., Grondal, C. & Raabe, G. Control of four stereocentres in a triple cascade organocatalytic reaction. Nature 441, 861–863 (2006).
Climent, M. J., Corma, A., Iborra, S. & Sabater, M. J. Heterogeneous catalysis for tandem reactions. ACS Catal. 4, 870–891 (2014).
Fraile, J. M., Mallada, R., Mayoral, J. A., Menéndez, M. & Roldán, L. Shift of multiple incompatible equilibriums by a combination of heterogeneous catalysis and membranes. Chem. Eur. J. 16, 3296–3299 (2010).
Wheeldon, I. et al. Substrate channelling as an approach to cascade reactions. Nat. Chem. 8, 299–309 (2016).
Fogg, D. E. & dos Santos, E. N. Tandem catalysis: a taxonomy and illustrative review. Coord. Chem. Rev. 248, 2365–2379 (2004).
Li, L. & Herzon, S. B. Temporal separation of catalytic activities allows anti-Markovnikov reductive functionalization of terminal alkynes. Nat. Chem. 6, 22–27 (2013).
Lohr, T. L. & Marks, T. J. Orthogonal tandem catalysis. Nat. Chem. 7, 477–482 (2015).
Singh, N. et al. Tandem reactions in self-sorted catalytic molecular hydrogels. Chem. Sci. 7, 5568–5572 (2016).
Zeidan, R. K., Hwang, S.-J. & Davis, M. E. Multifunctional heterogeneous catalysts: SBA-15-containing primary amines and sulfonic acids. Angew. Chem. Int. Ed. 45, 6332–6335 (2006).
Brunelli, N. A., Venkatasubbaiah, K. & Jones, C. W. Cooperative catalysis with acid–base bifunctional mesoporous silica: impact of grafting and co-condensation synthesis methods on material structure and catalytic properties. Chem. Mater. 24, 2433–2442 (2012).
Gianotti, E., Diaz, U., Velty, A. & Corma, A. Designing bifunctional acid–base mesoporous hybrid catalysts for cascade reactions. Catal. Sci. Technol. 3, 2677–2688 (2013).
Weng, Z., Yu, T. & Zaera, F. Synthesis of solid catalysts with spatially resolved acidic and basic molecular functionalities. ACS Catal. 8, 2870–2879 (2018).
Corma, A., Díaz, U., García, T., Sastre, G. & Velty, A. Multifunctional hybrid organic–inorganic catalytic materials with a hierarchical system of well-defined micro-and mesopores. J. Am. Chem. Soc. 132, 15011–15021 (2010).
Bass, J. D. & Katz, A. Bifunctional surface imprinting of silica: thermolytic synthesis and characterization of discrete thiol–amine functional group pairs. Chem. Mater. 18, 1611–1620 (2006).
Yu, X. et al. The effect of the distance between acidic site and basic site immobilized on mesoporous solid on the activity in catalyzing aldol condensation. J. Solid State Chem. 184, 289–295 (2011).
Margelefsky, E. L., Bendjériou, A., Zeidan, R. K., Dufaud, V. & Davis, M. E. Nanoscale organization of thiol and arylsulfonic acid on silica leads to a highly active and selective bifunctional, heterogeneous catalyst. J. Am. Chem. Soc. 130, 13442–13449 (2008).
Margelefsky, E. L., Zeidan, R. K. & Davis, M. E. Cooperative catalysis by silica-supported organic functional groups. Chem. Soc. Rev. 37, 1118–1126 (2008).
Gao, J., Zhang, X., Lu, Y., Liu, S. & Liu, J. Selective functionalization of hollow nanospheres with acid and base groups for cascade reactions. Chem. Eur. J. 21, 7403–7407 (2015).
Merino, E. et al. Synthesis of structured porous polymers with acid and basic sites and their catalytic application in cascade-type reactions. Chem. Mater. 25, 981–988 (2013).
Li, P. et al. Core–shell structured mesoporous silica as acid–base bifunctional catalyst with designated diffusion path for cascade reaction sequences. Chem. Commun. 48, 10541–10543 (2012).
Li, P. et al. Core–shell structured MgAl-LDO@Al-MS hexagonal nanocomposite: an all inorganic acid–base bifunctional nanoreactor for one-pot cascade reactions. J. Mater. Chem. A 2, 339–344 (2014).
Vernekar, D. & Jagadeesan, D. Tunable acid–base bifunctional catalytic activity of FeOOH in an orthogonal tandem reaction. Catal. Sci. Technol. 5, 4029–4038 (2015).
Huang, Y., Xu, S. & Lin, V. S. Y. Bifunctionalized mesoporous materials with site-separated Brønsted acids and bases: catalyst for a two-step reaction sequence. Angew. Chem. Int. Ed. 50, 661–664 (2011).
Yang, Y. et al. A yolk–shell nanoreactor with a basic core and an acidic shell for cascade reactions. Angew. Chem. Int. Ed. 51, 9164–9168 (2012).
Jun, S. W. et al. One-pot synthesis of magnetically recyclable mesoporous silica supported acid–base catalysts for tandem reactions. Chem. Commun. 49, 7821–7823 (2013).
Motokura, K. et al. An acidic layered clay is combined with a basic layered clay for one-pot sequential reactions. J. Am. Chem. Soc. 127, 9674–9675 (2005).
Corma, A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem. Rev. 95, 559–614 (1995).
Choudary, B. M., Ranganath, K. V., Pal, U., Kantam, M. L. & Sreedhar, B. Nanocrystalline MgO for asymmetric Henry and Michael reactions. J. Am. Chem. Soc. 127, 13167–13171 (2005).
Díez, V., Apesteguía, C. & Di Cosimo, J. Aldol condensation of citral with acetone on MgO and alkali-promoted MgO catalysts. J. Catal. 240, 235–244 (2006).
Shimizu, K.-i & Satsuma, A. Toward a rational control of solid acid catalysis for green synthesis and biomass conversion. Energy Environ. Sci. 4, 3140–3153 (2011).
Osatiashtiani, A., Durndell, L. J., Manayil, J. C., Lee, A. F. & Wilson, K. Influence of alkyl chain length on sulfated zirconia catalysed batch and continuous esterification of carboxylic acids by light alcohols. Green Chem. 18, 5529–5535 (2016).
Montero, J. M., Gai, P., Wilson, K. & Lee, A. F. Structure-sensitive biodiesel synthesis over MgO nanocrystals. Green Chem. 11, 265–268 (2009).
Ciddor, L., Bennett, J. A., Hunns, J. A., Wilson, K. & Lee, A. F. Catalytic upgrading of bio-oils by esterification. J. Chem. Technol. Biotechnol. 90, 780–795 (2015).
Chai, M., TU, Q., LU, M. & Yang, Y. J. Esterification pretreatment of free fatty acid in biodiesel production, from laboratory to industry. Fuel Process. Technol. 125, 106–113 (2014).
Xu, P.-F. & Wang, W. Catalytic Cascade Reactions (John Wiley, 2013).
Djakovitch, L., Dufaud, V. & Zaidi, R. Heterogeneous palladium catalysts applied to the synthesis of 2- and 2,3-functionalised indoles. Adv. Synth. Catal. 348, 715–724 (2006).
Peng, W.-H., Lee, Y.-Y., Wu, C. & Wu, K. C. W. Acid–base bi-functionalized, large-pored mesoporous silica nanoparticles for cooperative catalysis of one-pot cellulose-to-HMF conversion. J. Mater. Chem. 22, 23181–23185 (2012).
Takagaki, A., Ohara, M., Nishimura, S. & Ebitani, K. A one-pot reaction for biorefinery: combination of solid acid and base catalysts for direct production of 5-hydroxymethylfurfural from saccharides. Chem. Commun., 6276–6278 (2009).
Shang, F. et al. Direct synthesis of acid–base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions. J. Colloid Interface Sci. 355, 190–197 (2011).
Shiju, N. R., Alberts, A. H., Khalid, S., Brown, D. R. & Rothenberg, G. Mesoporous silica with site-isolated amine and phosphotungstic acid groups: a solid catalyst with tunable antagonistic functions for one-pot tandem reactions. Angew. Chem. Int. Ed. 50, 9615–9619 (2011).
Cohen, B. J., Kraus, M. A. & Patchornik, A. ‘Wolf and lamb’ reactions: equilibrium and kinetic effects in multipolymer systems. J. Am. Chem. Soc. 103, 7620–7629 (1981).
Chi, Y., Scroggins, S. T. & Fréchet, J. M. J. One-pot multi-component asymmetric cascade reactions catalyzed by soluble star polymers with highly branched non-interpenetrating catalytic cores. J. Am. Chem. Soc. 130, 6322–6323 (2008).
Parlett, C. M. et al. Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions. Nat. Mater. 15, 178–182 (2016).
Wei, Y. L., Wang, Y. M., Zhu, J. H. & Wu, Z. Y. In-situ coating of SBA-15 with MgO: direct synthesis of mesoporous solid bases from strong acidic systems. Adv. Mater. 15, 1943–1945 (2003).
Osatiashtiani, A. et al. Hydrothermally stable, conformal, sulfated zirconia monolayer catalysts for glucose conversion to 5-HMF. ACS Catal. 5, 4345–4352 (2015).
Zhang, Y., Liang, H., Zhao, C. Y. & Liu, Y. Macroporous alumina monoliths prepared by filling polymer foams with alumina hydrosols. J. Mater. Sci. 44, 931–938 (2009).
Di Cosimo, J. I., Díez, V. K., Ferretti, C. & Apesteguía, C. R. in Catalysis, Vol. 26 (eds Spivey J., Dooley, K. M. & Han, Y.-F.) 1–28 (Royal Society of Chemistry, 2014).
Pennycook, S. & Boatner, L. Chemically sensitive structure-imaging with a scanning transmission electron microscope. Nature 336, 565–567 (1988).
Robinson, N., Robertson, C., Gladden, L. F., Jenkins, S. J. & D’Agostino, C. Direct correlation between adsorption energetics and nuclear spin relaxation in a liquid-saturated catalyst material. ChemPhysChem 19, 2472–2479 (2018).
Isaacs, M. A. et al. Unravelling mass transport in hierarchically porous catalysts. J. Mater. Chem. A 7, 11814–11825 (2019).
Robinson, N. & D’Agostino, C. NMR investigation into the influence of surface interactions on liquid diffusion in a mesoporous catalyst support. Top. Catal. 63, 391–327 (2020).
Song, Y. Q. et al. T1–T2 correlation spectra obtained using a fast two-dimensional Laplace inversion. J. Magn. Reson. 154, 261–268 (2002).
Galarneau, A., Cambon, H., Di Renzo, F. & Fajula, F. True microporosity and surface area of mesoporous SBA-15 silicas as a function of synthesis temperature. Langmuir 17, 8328–8335 (2001).
Mitchell, J. et al. Validation of NMR relaxation exchange time measurements in porous media. J. Chem. Phys. 127, 234701 (2007).
Li, G., Xiao, J. & Zhang, W. Efficient and reusable amine-functionalized polyacrylonitrile fiber catalysts for Knoevenagel condensation in water. Green. Chem. 14, 2234–2242 (2012).
Chen, X., Arruebo, M. & Yeung, K. L. Flow-synthesis of mesoporous silicas and their use in the preparation of magnetic catalysts for Knoevenagel condensation reactions. Catal. Today 204, 140–147 (2013).
Sen, T., Tiddy, G., Casci, J. & Anderson, M. Synthesis and characterization of hierarchically ordered porous silica materials. Chem. Mater. 16, 2044–2054 (2004).
Wainwright, S. G. et al. True liquid crystal templating of SBA-15 with reduced microporosity. Micropor. Mesopor. Mat. 172, 112–117 (2013).
Mazumder, V. & Sun, S. Oleylamine-mediated synthesis of Pd nanoparticles for catalytic formic acid oxidation. J. Am. Chem. Soc. 131, 4588–4589 (2009).
Brun, N. et al. Hard macrocellular silica Si (HIPE) foams templating micro/macroporous carbonaceous monoliths: applications as lithium ion battery negative electrodes and electrochemical capacitors. Adv. Funct. Mater. 19, 3136–3145 (2009).
Akkerman, A. et al. Inelastic electron interactions in the energy range 50 eV to 10 keV in insulators: alkali halides and metal oxides. Phys. Status Solidi b 198, 769–784 (1996).
Platon, A. & Thomson, W. J. Quantitative Lewis/Brönsted ratios using DRIFTS. Ind. Eng. Chem. Res. 42, 5988–5992 (2003).
Farneth, W. E. & Gorte, R. J. Methods for characterizing zeolite acidity. Chem. Rev. 95, 615–635 (1995).
We thank the Australian Research Council for support (LP180100116, IC150100019, DP 200100204 and DP200100313). Electron microscopy access was provided through the Leeds EPSRC Nanoscience and Nanotechnology Research Equipment Facility (EP/K023853/1), the University of Birmingham Nanoscale Physics Laboratory and the Durham University G.J. Russell Microscopy Facility.
The authors declare no competing interests.
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(a) SEM micrograph, and (b) macropore size distribution from Hg intrusion porosimetry of SZ/MgO/MM-SBA-15. Corresponding normal and cumulative size distributions from SEM of (c) macropore diameter, and (d) macropore window diameter. Note that Hg intrusion measures macropore window size and not macropore diameter64.
(a) DRIFT spectra of saturated chemisorbed pyridine adlayers, (b) reactively-formed propene mass spectra following temperature-programmed desorption of chemisorbed propylamine and associated acid site loadings determined from accompanying TGA mass losses, and (c) CO2 mass spectra following temperature-programmed desorption of chemisorbed CO2 with base site loadings from CO2 pulse chemisorption over MM-SBA-15 materials.
Extended Data Fig. 3 Imaging of acid and base sites within spatially orthogonal acid–base catalyst using funtionalised Pt nanoparticles.
(a) HAADF-STEM, and (b) bright-field micrographs of SZ/MgO/MM-SBA-15 treated with 3-mercaptopropionic acid functionalised Pt NPs, and (c) corresponding area-averaged Pt concentrations determined by EDX within highlighted regions of HAADF-STEM image. Analogous (d) HAADF-STEM, (e) bright-field, and (f) corresponding area-averaged Pt concentrations determined by EDX for SZ/MgO/MM-SBA-15 treated with 4-aminothiophenol functionalised Pt NPs. (g) and (h) Raw EDX spectra associated with mesopore and macropore domains in images (c) and (f) respectively.
Extended Data Fig. 4 Catalytic performance of bifunctional nanoparticle catalyst containing co-located acid–base sites.
Tributyrin transesterification (TAG) with methanol in the absence or presence of hexanoic acid (FFA) over MgO/SZ and SZ nanoparticle catalysts, and simultaneous FFA esterification. Error bars represent S.D. of the mean (n = 3). Reaction conditions: 100 mg catalyst, 5 mmol tributyrin or a mixture of 5 mmol tributyrin/5 mol hexanoic acid, 60 cm3 methanol, 0.1 mmol dihexylether as an internal standard, 60 °C under air, 3 h reaction.
Extended Data Fig. 5 Catalytic performance of hierarchical porous catalysts in the cascade deacetalisation and condensation of dimethyl acetals.
Cyanoester yield from cascade deacetalisation and Knoevenagel condensation of benzaldehyde dimethyl acetal (BDMA), 2-furaldehyde dimethyl acetal (FDMA) or anisaldehyde dimethyl acetal (ADMA) with ethyl cyanoacetate after 6 h reaction over SZ/MgO/MM-SBA-15, a 1:1 by weight physical mixture of SZ/MM-SBA-15 and MgO/MM-SBA-15, or without catalyst. Reaction conditions: 25 mg catalyst (except for physical mixture where 25 mg each of monofunctional catalyst was used), 5 mmol dimethyl acetal, 50 mmol ethyl cyanoacetate, 5 mmol deionised water, 5 cm3 toluene, 1 mmol nonane as an internal standard, 50 °C under N2. Error bars represent S.D. of the mean (n = 2).
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Isaacs, M.A., Parlett, C.M.A., Robinson, N. et al. A spatially orthogonal hierarchically porous acid–base catalyst for cascade and antagonistic reactions. Nat Catal 3, 921–931 (2020). https://doi.org/10.1038/s41929-020-00526-5