Quantitative Kinetic Insights from Operando-UV/Vis Spectroscopy: An Application to NH3−SCR of NOx on Cu-CHA Catalysts
Dr. Chiara Negri
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (lead), Methodology (equal), Writing - original draft (lead)
Search for more papers by this authorDr. Nicola Usberti
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (equal), Formal analysis (equal), Validation (equal), Writing - original draft (equal)
Search for more papers by this authorGabriele Contaldo
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Conceptualization (supporting), Data curation (supporting), Investigation (supporting), Validation (supporting)
Search for more papers by this authorDr. Mauro Bracconi
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Formal analysis (equal), Methodology (equal), Software (lead), Writing - review & editing (equal)
Search for more papers by this authorProf. Isabella Nova
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (lead), Investigation (lead), Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Matteo Maestri
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Formal analysis (lead), Methodology (lead), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorCorresponding Author
Prof. Enrico Tronconi
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Conceptualization (lead), Formal analysis (lead), Investigation (lead), Writing - review & editing (lead)
Search for more papers by this authorDr. Chiara Negri
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (lead), Methodology (equal), Writing - original draft (lead)
Search for more papers by this authorDr. Nicola Usberti
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (equal), Formal analysis (equal), Validation (equal), Writing - original draft (equal)
Search for more papers by this authorGabriele Contaldo
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Conceptualization (supporting), Data curation (supporting), Investigation (supporting), Validation (supporting)
Search for more papers by this authorDr. Mauro Bracconi
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Formal analysis (equal), Methodology (equal), Software (lead), Writing - review & editing (equal)
Search for more papers by this authorProf. Isabella Nova
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Data curation (lead), Investigation (lead), Writing - review & editing (equal)
Search for more papers by this authorCorresponding Author
Prof. Matteo Maestri
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Formal analysis (lead), Methodology (lead), Supervision (lead), Writing - review & editing (lead)
Search for more papers by this authorCorresponding Author
Prof. Enrico Tronconi
Laboratory of Catalysis and Catalytic Processes, Dipartimento di Energia, Politecnico di Milano, Via La Masa 34, 20156 Milano, Italy
Contribution: Conceptualization (lead), Formal analysis (lead), Investigation (lead), Writing - review & editing (lead)
Search for more papers by this authorAbstract
We employ UV/Vis Diffuse Reflectance spectroscopy directly coupled with a packed bed flow reactor to extract quantitative kinetic information. We use as a show-case the CuII/CuI redox dynamics during the reduction half cycle of the NH3-Selective Catalytic Reduction (SCR) on Cu-CHA catalysts. Our measurements enable quantification of the fraction of oxidized Cu, reconstructed by Multivariate Curve Resolution (MCR) together with monitoring of the gas-phase evolution during the reaction. These data both on the dynamics of the gas-phase and of the active site oxidation state have been used to assess the reduction half cycle rate equation and estimate the rate constant. Our results in terms of reaction orders and kinetic constant are in line with previous findings in the literature. Overall, our results demonstrate that the combined analysis of the UV spectra and of the gas-phase dynamics provides converging and unparalleled kinetic insight: this approach effectively resolves ambiguities concerning RHC kinetics and mechanism. More in general, this work provides evidence that operando spectroscopy can be used to extract quantitative kinetic information on catalytic cycles.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
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References
- 1
- 1aA. Chakrabarti, M. E. Ford, D. Gregory, R. Hu, C. J. Keturakis, S. Lwin, Y. Tang, Z. Yang, M. Zhu, M. A. Bañares, I. E. Wachs, Catal. Today 2017, 283, 27–53;
- 1bL. Chen, X. Ding, Z. Wang, S. Xu, Q. Jiang, C. Dun, J. J. Urban, Surf. Sci. and Technol. 2024, 2, 9;
10.1007/s44251-024-00038-5 Google Scholar
- 1cE. Groppo, S. Rojas-Buzo, S. Bordiga, Chem. Rev. 2023, 123, 12135–12169;
- 1dM. A. Bañares, M. Daturi, Catal. Today 2023, 423, 114255.
- 2M. A. Bañares, Catal. Today 2005, 100, 71–77.
- 3
- 3aA. Godiksen, F. N. Stappen, P. N. R. Vennestrom, F. Giordanino, S. B. Rasmussen, L. F. Lundegaard, S. Mossin, J. Phys. Chem. C 2014, 118, 23126–23138;
- 3bC. Lamberti, A. Zecchina, E. Groppo, S. Bordiga, Chem. Soc. Rev. 2010, 39, 4951–5001;
- 3cC. Paze, S. Bordiga, C. Lamberti, M. Salvalaggio, A. Zecchina, G. Bellussi, J. Phys. Chem. B 1997, 101, 4740–4751.
- 4
- 4aC. Ciardelli, I. Nova, E. Tronconi, D. Chatterjee, B. Bandl-Konrad, Chem. Commun. 2004, 2718–2719;
- 4bM. Colombo, I. Nova, E. Tronconi, Catal. Today 2012, 197, 243–255;
- 4cI. Nova, C. Ciardelli, E. Tronconi, D. Chatterjee, B. Bandl-Konrad, Catal. Today 2006, 114, 3–12;
- 4dI. Nova, E. Tronconi, H.-Y. Chen, in Urea-SCR Technology for deNOx After Treatment of Diesel Exhausts (Ed.: 2014), Springer New York, pp. 123–147.
10.1007/978-1-4899-8071-7 Google Scholar
- 5
- 5aP. M. Abdala, O. V. Safonova, G. Wiker, W. van Beek, H. Emerich, J. A. van Bokhoven, J. Sa, J. Szlachetko, M. Nachtegaal, Chimia 2012, 66, 699–705;
- 5bL. v Beek, D. Jain, P. Gholkar, T. J. Eldridge, H. P. Nguyen, K. Muramoto, A. Urakawa, Catal. Today 2024, 429 ;
- 5cM. H. Groothaert, K. Lievens, H. Leeman, B. M. Weckhuysen, R. A. Schoonheydt, J. Catal. 2003, 220, 500–512;
- 5dG. Guilera, B. Gorges, S. Pascarelli, H. Vitoux, M. A. Newton, C. Prestipino, Y. Nagai, N. Hara, J. Synchrotron Radiat. 2009, 16, 628–634;
- 5eA. Maghsoumi, A. Ravanelli, F. Consonni, F. Nanni, A. Lucotti, M. Tommasini, A. Donazzi, M. Maestri, React. Chem. Eng. 2017, 2, 908–918.
- 6
- 6aE. Borfecchia, C. Negri, K. A. Lomachenko, C. Lamberti, T. V. Janssens, G. Berlier, React. Chem. Eng. 2019, 4, 1067–1080;
- 6bA. de Juan, J. Jaumot, R. A. Tauler, Anal. Methods 2014, 6, 4964–4976;
- 6cA. Martini, E. Alladio, E. Borfecchia, Top. Catal. 2018, 61, 1396–1407;
- 6dJ. Goetze, F. Meirer, I. Yarulina, J. Gascon, F. Kapteijn, J. Ruiz-Martínez, B. M. Weckhuysen, ACS Catal. 2017, 7, 4033–4046;
- 6eH. Ma, J. Gopakumar, W. Zhang, S. K. Regli, Y. Wang, K. R. Rout, T. Fuglerud, M. Piccinini, M. Rønning, D. Chen, Ind. Eng. Chem. Res. 2021, 60, 9437–9447.
- 7
- 7aM. Zhu, J.-K. Lai, U. Tumuluri, M. E. Ford, Z. Wu, I. E. Wachs, ACS Catal. 2017, 7, 8358–8361;
- 7bH. Kubota, C. Liu, T. Amada, K. Kon, T. Toyao, Z. Maeno, K. Ueda, A. Satsuma, N. Tsunoji, T. Sano, K. Shimizu, Catal. Today 2021, 376, 73–80;
- 7cC. Liu, H. Kubota, T. Amada, T. Toyao, Z. Maeno, M. Ogura, N. Nakazawa, S. Inagaki, Y. Kubota, K.-i. Shimizu, Catal. Sci. Technol. 2021, 11, 4459–4470;
- 7dC. Liu, H. Kubota, T. Amada, K. Kon, T. Toyao, Z. Maeno, K. Ueda, J. Ohyama, A. Satsuma, T. Tanigawa, N. Tsunoji, T. Sano, K.-i. Shimizu, ChemCatChem 2020, 12, 3050–3059.
- 8E. Borfecchia, P. Beato, S. Svelle, U. Olsbye, C. Lamberti, S. Bordiga, Chem. Soc. Rev. 2018, 47, 8097–8133.
- 9
- 9aS. H. Krishna, A. Goswami, Y. Wang, C. B. Jones, D. P. Dean, J. T. Miller, W. F. Schneider, R. Gounder, Nat. Catal. 2023, 6, 276–285;
- 9bC. B. Jones, I. Khurana, S. H. Krishna, A. J. Shih, W. N. Delgass, J. T. Miller, F. H. Ribeiro, W. F. Schneider, R. Gounder, J. Catal. 2020, 389, 140–149.
- 10C. Negri, R. Colombo, M. Bracconi, C. Atzori, A. Donazzi, A. Lucotti, M. Tommasini, M. Maestri, Catal. Sci. Technol. 2024, 14, 1318–1327.
- 11N. D. Nasello, U. Iacobone, N. Usberti, A. Gjetja, I. Nova, E. Tronconi, R. Villamaina, M. P. Ruggeri, D. Bounechada, A. P. E. York, J. Collier, ACS Catal. 2024, 14, 4265–4276.
- 12
- 12aW. Hu, F. Gramigni, N. D. Nasello, N. Usberti, U. Iacobone, S. Liu, I. Nova, X. Gao, E. Tronconi, ACS Catal. 2022, 12, 5263–5274;
- 12bR. Daya, D. Trandal, U. Menon, D. J. Deka, W. P. Partridge, S. Y. Joshi, ACS Catal. 2022, 12, 6418–6433;
- 12cF. Gramigni, N. D. Nasello, N. Usberti, U. Iacobone, T. Selleri, W. Hu, S. Liu, X. Gao, I. Nova, E. Tronconi, ACS Catal. 2021, 11, 4821–4831.
- 13
- 13aF. Giordanino, P. N. R. Vennestrom, L. F. Lundegaard, F. N. Stappen, S. Mossin, P. Beato, S. Bordiga, C. Lamberti, Dalton Trans. 2013, 42, 12741–12761;
- 13bH. Li, C. Paolucci, I. Khurana, L. Wilcox, F. Goltl, J. D. Albarracin-Caballero, A. J. Shih, F. H. Ribeiro, R. Gounder, W. F. Schneider, Chem. Sci. 2019, 10, 2373–2384;
- 13cM. L. Bols, J. Ma, F. Rammal, D. Plessers, X. Wu, S. Navarro-Jaén, A. J. Heyer, B. F. Sels, E. I. Solomon, R. A. Schoonheydt, Chem. Rev. 2024, 124, 2352–2418;
- 13dC. Negri, M. Signorile, N. G. Porcaro, E. Borfecchia, G. Berlier, T. V. Janssens, S. Bordiga, Appl. Catal. A 2019, 578, 1–9.
- 14C. Negri, E. Borfecchia, M. Cutini, K. A. Lomachenko, T. V. Janssens, G. Berlier, S. Bordiga, ChemCatChem 2019, 11, 3828–3838.
- 15
- 15aL. N. Trevani, J. C. Roberts, P. R. Tremaine, J. Solution Chem. 2001, 30, 585–622;
- 15bY. Ohata, H. Kubota, T. Toyao, K.-i. Shimizu, T. Ohnishi, T. Moteki, M. Ogura, Catal. Sci. Technol. 2021, 11, 2718–2733.
- 16C. Negri, T. Selleri, E. Borfecchia, A. Martini, K. A. Lomachenko, T. V. Janssens, M. Cutini, S. Bordiga, G. Berlier, J. Am. Chem. Soc. 2020, 142, 15884–15896.
- 17
- 17aP. Chen, D. E. Root, C. Campochiaro, K. Fujisawa, E. I. Solomon, J. Am. Chem. Soc. 2003, 125, 466–474;
- 17bH. M. Rhoda, D. Plessers, A. J. Heyer, M. L. Bols, R. A. Schoonheydt, B. F. Sels, E. I. Solomon, J. Am. Chem. Soc. 2021, 143, 7531–7540;
- 17cE. I. Solomon, Inorg. Chem. 2006, 45, 8012–8025;
- 17dP. J. Smeets, J. S. Woertink, B. F. Sels, E. I. Solomon, R. A. Schoonheydt, Inorg. Chem. 2010, 49, 3573–3583.
- 18C. K. Jørgensen, in Progress in Inorganic Chemistry,, Vol. 4 Ch. 2 (Ed.: F. A. Cotton), John Wiley & Sons, Hoboken, NJ, USA 2007.
- 19G. Contaldo, M. Ferri, C. Negri, I. Nova, M. Maestri, E. Tronconi, ChemCatChem 2023, 15.
- 20F. C. Jentoft, Adv. Catal. 2009, 52, 129–211.
- 21F. C. Meunier, React. Chem. Eng. 2016, 1, 134–141.
- 22R. Tauler, Chemom. Intell. Lab. Syst. 1995, 30, 133–146.
- 23A. de Juan, R. Tauler, Anal. Chim. Acta. 2003, 500, 195–210.
- 24W. Windig, C. E. Heckler, F. A. Agblevor, R. J. Evans, Chem. Int. Lab. Syst. 1992, 14, 195–207.
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