Barolo, C.

Bonomo, M.

Bordiga, S.

Centrella, B.

Finelli, V.

Mariotti, N.

Signorile, M.

English

Institutional Research Information System University of Turin

Catalysis and sustainability: Beside the classical parameters employed to determine the efficiency ofa catalytic process (i.e. turnover number (TON), turnover frequency (TOF)…),other aspects should be introduced. In particular (i) the environmental andeconomic sustainability and (ii) the recyclability of the catalysts. Processsustainability Is crucial, both in laboratory and in industrial scale. To assessthe sustainability of a process, it is necessary to consider all the life-cyclephases: firstly, the row material selection, then, the sustainability of thesynthetic process, and finally the recyclability of the obtained catalyst.1,2A sustainability-driven approach for the comparison of heterogenous and homogenous Cu-based catalysts in the DMTM reaction Barbara Centrella, Nicole Mariotti, Matteo Bonomo, Valeria Finelli, Matteo Signorile, Silvia Bordiga, Claudia BaroloDepartment of Chemistry and NIS Interdepartmental Centre, University of Turin, Via Pietro Giuria 7, 10125 Torino, Italy email: barbara.centrella@unito.it How to assess sustainability?Copper-based catalystSUSTAINABLE MATERIALRELIABLE AND SECURE(Society)CLEAN(Environment)AFFORDABLE(Economic)LIFE-CYCLE PHASESRAWMATERIALS(+) Low Supply risk(-)Low substitutability(https://www.rsc.org/periodic-table/element/29/copper)(+) Low CED (53.7 MJ-eq/Kg)(+) $9.78/kg(https://mineralprices.com/base-metals/)MATERIALSPRODUCTIONSolvents and materials involved in the final material production should be safe and non toxicGreen metricsSynthesis LCAGHG emissions*Materials costs, energy costs, production scale**USELeakages, durabilityLCA/EnvironmentLCA/EfficiencyEND OF LIFE ToxicityRecovery, recyclingWaste management costs**https://it.vwr.com/store/ LAB-SCALE*https://www.eea.europa.eu/Case study: preliminary sustainability assessment of two potential catalysts for DMTM Homogeneous catalyst5 Heterogeneous catalyst6+Material Quantity Cost Cost/€ CO2eq/g6,6′-Dimethyl-2,2′-dipyridyl0,67 g 47 €/g 31,49[Cu(CH3CN)4] (PF6) 0,64 g 16,2 €/g 10,37Solvent 10 mL 0,005 €/mL 0,053h, r.t. 0,01 Kwh 0,082 €/kWh <0,01 3,524N2 atm 2 mol 2,75E-05 €/mol <0,01Material Quantity Cost Cost/€ CO2eq/gZrCl4 0,73 g 0,48 €/g 0,35H2BPDC 0,68 g 7,68 €/g 5,22H2BPyDC66'dme 0,08 g 360 €/g 36,05Benzoic Acid 1,15 g 0,16 €/g 0,18DMF 42,63 mL 0,06 €/mL 2,45Acetone–work up 25,87 mL 0,009 €/mL 0,22[Cu(CH3CN)4] (PF6) 0,105 g 16,20 €/g 1,70130° C, 24 h 60,9 kWh 0,08 €/kWh 5,00 14049,6310% of bipy linker90% of dicarboxylic linker41,9 €/g305,71 €Cost for the same amount of copper sites41,9 €49,48 €/gCost per gramActive copper sites per gram6 1,73 mmol 0,28 mmolZrZrZrZrZrZrDirect Methane To Methanol challenge4: road toward the perfect catalystAiming at a preliminary comparison we select a copper complex as homogenous catalyst, (left side) whoseligands are suitable for the construction of a MOF as heterogeneous catalyst, (right side) to obtain twochemically comparable catalysts as potential candidates for DMTM. This sustainability-driven comparisonhas been conducted following two different approaches: (i) the cost per gram of catalyst and (ii) the costper active site. The second evaluation is necessary since the proposed MOF contains only 10% of thecomplex’s linkers, and consequently a limited quantity of copper centers.Bibliography:1 Sheldon, R. A. Metrics of Green Chemistry and Sustainability: Past, Present, and Future. ACS Sustain. Chem. Eng. 6, (2018)2 Ashby, M. Materials and sustainable development. Materials and Sustainable Development (2015)3 Byggeth, S.; Broman, G.;  Robèrt, K. H. vol. 15, (2007) 4 Han, B.; Yang, Y.; Xu, Y.; Etim, U. J.; Qiao, K.; Xu, B.; Yan, Z.; Chinese J. Catal., 37 (8), (2016)5 Listorti, A.; Accorsi, G.; Rio, Y.; Armaroli, N.; Moudam, O.; Gégout, A.; Delavaux-Nicot, B.; Holler, M.; Nierengarten, J. F. ; Inorg. Chem. (2008)6 Kaur, PhD thesis; Optimization of UiO-67 type Metal-Organic Framework for Catalysis, (2020)7 Braglia, L.; Borfecchia, E.; Maddalena, L; Øien, S.; Lomachenko, K. A.; Bugaev, A. L.; Bordiga, S.; Soldatov, A. V; Lillerud, K. P.; Lamberti, C.; Catalysis Today, Volume 283, (2017)8 Rebitzer, G. Integrating, Seuring, S., Goldbach, M., Eds.; Physica- Verlag HD: Heidelberg, (2002)Cost for the same amount of copper sitesCost per gramActive copper sites per gram6Take-home message:The proposed analysis could represent the starting point of a go/no-go criteria.• Similar cost in terms of euro/g• Significant dilution of the copper in MOF implies a factor of 7 when the cost isnormalizes to the amount of copper• Urgent need to evaluate activity and recyclability of the catalysts.• A reduction up to 70%8 of the environmental impacts are foreseen identifying thesustainability hotspots of both the synthetic procedures.The heterogenous catalysts (i.e. the MOF) would be preferred if it would be proved tobe at least 7 times more active than the homogenous catalyst (copper complex).“It is important to include sustainability aspects in decision making at the product development stage, especially early in the development process”3Nowadays, it is a go/no-go aspectMATERIALS SELECTIONRaw materialsSYNTHESISAuxiliaries and processesUSE PHASESelectivity, efficiency (TON, TOF)END OF LIFERecyclability● Element availability● Source (Fossil vs. Bio-based)● Toxicity● CostNEW EMERGING MATERIALS CONSTRAINTSWhat is usually considered?● 12 Green Chemistry Principles (Guideline)● Green metrics● Eco-scale (It considers costs)● Life Cycle AssessmentWhat is usually considered?Desirable catalystsSustainable and cheap synthesis Excellent activity and selectivityRecyclability Thehomogeneouscatalyst is about 7 times cheaper!

A sustainability-driven approach for the comparison of heterogeneous and homogeneous Cu-based catalysts in the DMTM reaction

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A sustainability-driven approach for the comparison of heterogeneous and homogeneous Cu-based catalysts in the DMTM reaction

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