Alfonso GRASSI | SUSTAINABLE CATALYSIS

cod. 0522300045

SUSTAINABLE CATALYSIS

	0522300045
	DEPARTMENT OF CHEMISTRY AND BIOLOGY "ADOLFO ZAMBELLI"
	EQF7
	CHEMISTRY
	2020/2021

CURRICULUM SUSTAINABLE CHEMISTRY

	OBBLIGATORIO
	YEAR OF COURSE 1
	YEAR OF DIDACTIC SYSTEM 2016
	SECONDO SEMESTRE

TEACHING UNITS

	SSD	CFU	HOURS	ACTIVITY	TYPE OF ACTIVITY
	CHIM/03	12	96	LESSONS	COMPULSORY SUBJECTS, CHARACTERISTIC OF THE CLASS

PROFESSORS

	CLAUDIO PELLECCHIA T Curriculum
	CARMINE CAPACCHIONE Curriculum
	ALFONSO GRASSI Curriculum

	Objectives
	TEACHING WILL CONSIST OF LECTURES IN THE CLASSROOM. THE STUDENTS WILL BE INTRODUCED TO THE GENERAL PRINCIPLES OF GREEN CHEMISTRY AND CRITERIA FOR THE SUSTAINABILITY OF CHEMICAL REACTIONS CARRIED OUT AT LAB AND INDUSTRIAL PLANT SCALE. THE MAIN HETEROGENEOUS AND HOMOGENEOUS CATALYTIC PROCESSES, CARRIED OUT IN INDUSTRY UNDER SUSTAINABLE CONDITIONS AND EMPLOYING BIOSOURCED PLATFORM MOLECULES, WILL BE ILLUSTRATED AND DISCUSSED. PARTICULAR ATTENTION WILL BE DEVOTED TO THE SYNTHESIS OF POLYMERS RESULTING FROM BIOSOURCED MONOMERS AND THAT ALLOW A REDUCTION IN CO2 EMISSION IN ATMOSPHERE. THE MAIN ACQUIRED KNOWLEDGE WILL BE: •CRITERIA FOR THE SUSTAINABILITY OF CHEMICAL REACTIONS. •METHODS FOR THE SYNTHESIS OF HETEROGENEOUS AND HOMEGENOUS METAL CATALYSTS AND THEIR ROLE IN THE MAIN EXAMPLES OF CHEMICAL REACTIONS (OXIDATION, REDUCTION, ACID AND BASE CATALYZED, C-C BOND FORMING) OF INTEREST FOR INDUSTRY. •HOMOGENEOUS AND HETEROGENEOUS CATALYTIC PROCESSES SUITABLE FOR THE SYNTHESIS OF PLATFORM MOLECULES AND PRODUCTS OF INTEREST FOR A GREEN INDUSTRY. THE MAIN CAPABILITIES WILL BE: •TO DESIGN A GREEN SYNTHESIS OF PLATFORM MOLECULES OF INTEREST FOR INDUSTRY. •TO EVALUATE THE ENVIRONMENTAL IMPACT (GREENESS) OF A CHEMICAL REACTION. •TO DESIGN NEW REACTION PATHWAYS FOR A SUSTAINABLE CHEMISTRY.

TEACHING WILL CONSIST OF LECTURES IN THE CLASSROOM. THE STUDENTS WILL BE INTRODUCED TO THE GENERAL PRINCIPLES OF GREEN CHEMISTRY AND CRITERIA FOR THE SUSTAINABILITY OF CHEMICAL REACTIONS CARRIED OUT AT LAB AND INDUSTRIAL PLANT SCALE. THE MAIN HETEROGENEOUS AND HOMOGENEOUS CATALYTIC PROCESSES, CARRIED OUT IN INDUSTRY UNDER SUSTAINABLE CONDITIONS AND EMPLOYING BIOSOURCED PLATFORM MOLECULES, WILL BE ILLUSTRATED AND DISCUSSED. PARTICULAR ATTENTION WILL BE DEVOTED TO THE SYNTHESIS OF POLYMERS RESULTING FROM BIOSOURCED MONOMERS AND THAT ALLOW A REDUCTION IN CO2 EMISSION IN ATMOSPHERE.

THE MAIN ACQUIRED KNOWLEDGE WILL BE:
•CRITERIA FOR THE SUSTAINABILITY OF CHEMICAL REACTIONS.
•METHODS FOR THE SYNTHESIS OF HETEROGENEOUS AND HOMEGENOUS METAL CATALYSTS AND THEIR ROLE IN THE MAIN EXAMPLES OF CHEMICAL REACTIONS (OXIDATION, REDUCTION, ACID AND BASE CATALYZED, C-C BOND FORMING) OF INTEREST FOR INDUSTRY.
•HOMOGENEOUS AND HETEROGENEOUS CATALYTIC PROCESSES SUITABLE FOR THE SYNTHESIS OF PLATFORM MOLECULES AND PRODUCTS OF INTEREST FOR A GREEN INDUSTRY.

THE MAIN CAPABILITIES WILL BE:
•TO DESIGN A GREEN SYNTHESIS OF PLATFORM MOLECULES OF INTEREST FOR INDUSTRY.
•TO EVALUATE THE ENVIRONMENTAL IMPACT (GREENESS) OF A CHEMICAL REACTION.
•TO DESIGN NEW REACTION PATHWAYS FOR A SUSTAINABLE CHEMISTRY.

	Prerequisites
	KNOWLEDGE OF INORGANIC CHEMISTRY AND COORDINATION CHEMISTRY

	Contents
	PART 1 (PROF. A. GRASSI) PRINCIPLES OF GREEN CHEMISTRY. ASSESSMENT OF A CATALYTIC PROCESS SUSTAINABILITY: ATOM ECONOMY; E-FACTOR; CARBON FOOTPRINT; LIFE CYCLE ASSESSMENT. CATALYSIS IN GREEN SOLVENTS: WATER, BIPHASIC AQUEOUS SYSTEMS, MULTI-PHASE SYSTEMS; IONIC LIQUIDS. MICROWAVES IN CATALYSIS. BIOREFINERY. BIOMASS OF FIRST, SECOND AND THIRD GENERATION. PLATFORM MOLECULES FROM RENEWABLE RESOURCES. BIOETHANOL. FURANICS. GLYCEROL. DROP IN SYNTHESIS OF OLEFINS. HETEROGENOUS CATALYSIS BY SOLID ACIDS AND BASES. CLAYS AND ZEOLITES, SULPHONATED POLYMERS, HYDROTALCITES. SUPPORTED CATALYSTS ON MODIFIED SILICA. SUPPORTED METAL CATALYSTS. HETEROGENIZATION OF HOMOGENOUS CATALYSTS. INDUSTRIAL PROCESSES CATALYZED BY SOLID ACID AND BASES. REDUCTION REACTIONS CATALYZED BY METALS SUPPORTED ON INORGANICS AND POLYMERIC MATRICES. SYNTHESIS AND CHARACTERIZATION OF METAL NANOPARTICLES. HYDROGENATION AND HYDROGENOLYSIS. HYDROGEN FROM RENEWABLE SOURCES. WATER SPLITTING REACTION. HYDROGEN BORROWING. REDUCTION REACTIONS WITH SYSTEMS ALTERNATIVE TO HYDROGEN. NOBLE METAL NANOPARTICLES IN SUSTAINABLE CATALYSIS. ALKANE OXIDATION. OLEFIN EPOXIDATION. ALCOHOL AND POLYOLS OXIDATION. HYDROAMINATION. NITROARENES REDUCTION. PART 2 (PROF. C. PELLECCHIA) • ELEMENTARY STEPS OF THE CATALYTIC CYCLES: NUCLEOFILIC SUBSTITUTION; INSERTION AND ELIMINATION REACTIONS ; OXIDATIVE ADDITION - REDUCTIVE ELIMINATION. EFFICIENCY PARAMETERS OF THE CATALYTIC CYCLE (TO, TOF, TON). PRINCIPLES OF ASYMMETRIC CATALYSIS. MECHANISMS OF ENANTIOSELECTIVE CATALYSIS: CURTIN-HAMMET REGIME. REACTIVITY OF METAL-CARBON BOND. (7 H) • SELECTED EXAMPLES OF REACTIONS CATALIZED BY METALLIC COMPLEXES, WITH REFERENCES TO THE MOST RECENT STUDIES FOR THE DEVELOPMENT OF "SUSTAINABLE" CATALYSTS (USE OF NON-PRECIOUS METALS, USE OF "GREEN" SOLVENTS, USE OF RENEWABLE SOURCES, ETC.): • HYDROGENATION AND RELATED REACTIONS (HYDROXYLATION, HYDRO-CYANATION). (7 H) • HYDROFORMYLATION. (3 H) • CARBONYLATION. OXIDE WACKER OXIDATION. (3 H) • METATHESIS; (2 H) • POLYMERIZATION AND OLIGOMERISATION OF OLEPHINS AND OTHER HYDROCARBON MONOMERS. STEREOSPECIFIC POLYMERIZATION. METALLOCENE AND POST-METALLOCENE CATALYSTS. (7 H) • RING OPENING POLYMERIZATION (ROP) OF CYCLIC ESTERS FOR THE PRODUCTION OF ALIPHATIC POLYESTERS FROM RENEWABLE SOURCES. (2 H) • CO-POLYMERIZATION (ROCOP) OF EPOXIDES AND ORGANIC ANHYDRIDES. (1 H) • ACTIVATIONS OF ALKANES. SHILOV CATALYSTS FOR METHANOL SYNTHESIS FROM METHANE AND RELATED REACTIONS. (2 H) PART 3 (PROF. C. CAPACCHIONE) VALORIZATION OF CARBON DIOXIDE: REDUCTION OF CARBON DIOXIDE: SINTHESYS OF METHANOL, FORMALDEHYDE AND FORMIC ACID AND ITS DERIVATIVES BY CO2 REDUCTION. STHESYS OF CARBONATES AND POLYCARBONATES BY REACTION OF CO2 WITH EPOXIDES. REACTION OF CO2 WITH DOUBLE AND TRIPLE BONDS: SYNTHESIS OF ACRYLIC ACID AND ACRYLATES. POLYMERS BY REACTION OF CO2 WITH BUTADIENE. OTHER REACTIONS WITH CARBON DIOXIDE. MOLECULAR OXYGEN OR H2O2 AS OXIDIZING AGENT. IRON BIOMIMETIC CATALYSTS FOR THE OXIDATION OF ORGANIC MOLECULES WITH H2O2. A CASE OF INDUSTRIAL GREEN CHEMISTRY: THE OXIDATION OF XYLENE TO TEREPHTHALIC ACID. CATALYSIS WITH NON ENDANGERED METALS. FORMATION OF C-C AND C-HETEROATOM BONDS FROM PALLADIUM TO CATALYSIS WITH EARTH'S CRUST ABUNDANT METALS: FE, CU, AL, TI.

Contents

PART 1 (PROF. A. GRASSI)

PRINCIPLES OF GREEN CHEMISTRY. ASSESSMENT OF A CATALYTIC PROCESS SUSTAINABILITY: ATOM ECONOMY; E-FACTOR; CARBON FOOTPRINT; LIFE CYCLE ASSESSMENT. CATALYSIS IN GREEN SOLVENTS: WATER, BIPHASIC AQUEOUS SYSTEMS, MULTI-PHASE SYSTEMS; IONIC LIQUIDS. MICROWAVES IN CATALYSIS. BIOREFINERY. BIOMASS OF FIRST, SECOND AND THIRD GENERATION. PLATFORM MOLECULES FROM RENEWABLE RESOURCES. BIOETHANOL. FURANICS. GLYCEROL. DROP IN SYNTHESIS OF OLEFINS.
HETEROGENOUS CATALYSIS BY SOLID ACIDS AND BASES. CLAYS AND ZEOLITES, SULPHONATED POLYMERS, HYDROTALCITES. SUPPORTED CATALYSTS ON MODIFIED SILICA. SUPPORTED METAL CATALYSTS. HETEROGENIZATION OF HOMOGENOUS CATALYSTS. INDUSTRIAL PROCESSES CATALYZED BY SOLID ACID AND BASES.
REDUCTION REACTIONS CATALYZED BY METALS SUPPORTED ON INORGANICS
AND POLYMERIC MATRICES. SYNTHESIS AND CHARACTERIZATION OF METAL NANOPARTICLES. HYDROGENATION AND HYDROGENOLYSIS. HYDROGEN FROM RENEWABLE SOURCES. WATER SPLITTING REACTION. HYDROGEN BORROWING. REDUCTION REACTIONS WITH SYSTEMS ALTERNATIVE TO HYDROGEN.
NOBLE METAL NANOPARTICLES IN SUSTAINABLE CATALYSIS. ALKANE OXIDATION. OLEFIN EPOXIDATION. ALCOHOL AND POLYOLS OXIDATION. HYDROAMINATION. NITROARENES REDUCTION.

PART 2 (PROF. C. PELLECCHIA)

• ELEMENTARY STEPS OF THE CATALYTIC CYCLES: NUCLEOFILIC SUBSTITUTION; INSERTION AND ELIMINATION REACTIONS ; OXIDATIVE ADDITION - REDUCTIVE ELIMINATION. EFFICIENCY PARAMETERS OF THE CATALYTIC CYCLE (TO, TOF, TON). PRINCIPLES OF ASYMMETRIC CATALYSIS. MECHANISMS OF ENANTIOSELECTIVE CATALYSIS: CURTIN-HAMMET REGIME. REACTIVITY OF METAL-CARBON BOND. (7 H)
• SELECTED EXAMPLES OF REACTIONS CATALIZED BY METALLIC COMPLEXES, WITH REFERENCES TO THE MOST RECENT STUDIES FOR THE DEVELOPMENT OF "SUSTAINABLE" CATALYSTS (USE OF NON-PRECIOUS METALS, USE OF "GREEN" SOLVENTS, USE OF RENEWABLE SOURCES, ETC.):
• HYDROGENATION AND RELATED REACTIONS (HYDROXYLATION, HYDRO-CYANATION). (7 H)
• HYDROFORMYLATION. (3 H)
• CARBONYLATION. OXIDE WACKER OXIDATION. (3 H)
• METATHESIS; (2 H) •
POLYMERIZATION AND OLIGOMERISATION OF OLEPHINS AND OTHER HYDROCARBON MONOMERS. STEREOSPECIFIC POLYMERIZATION. METALLOCENE AND POST-METALLOCENE CATALYSTS. (7 H)
• RING OPENING POLYMERIZATION (ROP) OF CYCLIC ESTERS FOR THE PRODUCTION OF ALIPHATIC POLYESTERS FROM RENEWABLE SOURCES. (2 H)
• CO-POLYMERIZATION (ROCOP) OF EPOXIDES AND ORGANIC ANHYDRIDES. (1 H)
• ACTIVATIONS OF ALKANES. SHILOV CATALYSTS FOR METHANOL SYNTHESIS FROM METHANE AND RELATED REACTIONS. (2 H)

PART 3 (PROF. C. CAPACCHIONE)

VALORIZATION OF CARBON DIOXIDE: REDUCTION OF CARBON DIOXIDE: SINTHESYS OF METHANOL, FORMALDEHYDE AND FORMIC ACID AND ITS DERIVATIVES BY CO2 REDUCTION.
STHESYS OF CARBONATES AND POLYCARBONATES BY REACTION OF CO2 WITH EPOXIDES.
REACTION OF CO2 WITH DOUBLE AND TRIPLE BONDS: SYNTHESIS OF ACRYLIC ACID AND ACRYLATES. POLYMERS BY REACTION OF CO2 WITH BUTADIENE.
OTHER REACTIONS WITH CARBON DIOXIDE.
MOLECULAR OXYGEN OR H2O2 AS OXIDIZING AGENT.
IRON BIOMIMETIC CATALYSTS FOR THE OXIDATION OF ORGANIC MOLECULES WITH H2O2.
A CASE OF INDUSTRIAL GREEN CHEMISTRY: THE OXIDATION OF XYLENE TO TEREPHTHALIC ACID.
CATALYSIS WITH NON ENDANGERED METALS.
FORMATION OF C-C AND C-HETEROATOM BONDS FROM PALLADIUM TO CATALYSIS WITH EARTH'S CRUST ABUNDANT METALS: FE, CU, AL, TI.

	Teaching Methods
	THE TEACHING COURSE CONSISTS OF THREE MODULES OF 32 HOURS OF LECTURES EACH, AIDED BY MULTIMEDIA PRESENTATIONS, FOR A TOTAL OF 92 HOURS.

	Verification of learning
	ACHIEVING THE OBJECTIVES OF LEARNING IS VERIFIED BY EXAMINATION WITH AN EVALUATION IN THIRTIETH. THE EXAMINATION PROVIDES WRITTEN TESTS DURING THE COURSE (OPTIONAL). IF THE STUDENT PASSES THE WRITTEN TEST, THE STUDENT DOES NOT HAVE TO ATTEND THE FINAL TEST. THE FINAL EXAMINATION CONSISTS IN A WRITTEN COMPREHENSIVE EXAM. IF NECESSARY, IN THE OPINION OF THE TUTORING COMMISSION, THE WRITTEN EXAMINATION WILL BE INTEGRATED BY AN ORAL EXAM.

Verification of learning

ACHIEVING THE OBJECTIVES OF LEARNING IS VERIFIED BY EXAMINATION WITH AN EVALUATION IN THIRTIETH. THE EXAMINATION PROVIDES WRITTEN TESTS DURING THE COURSE (OPTIONAL). IF THE STUDENT PASSES THE WRITTEN TEST, THE STUDENT DOES NOT HAVE TO ATTEND THE FINAL TEST. THE FINAL EXAMINATION CONSISTS IN A WRITTEN COMPREHENSIVE EXAM. IF NECESSARY, IN THE OPINION OF THE TUTORING COMMISSION, THE WRITTEN EXAMINATION WILL BE INTEGRATED BY AN ORAL EXAM.

	Texts
	R.A SHELDON, I. ARENDS, U. HANEFELD “GREEN CHEMISTRY AND CATALYSIS” WILEY-VCH ED. P.T. ANASTS “GREEN CATALYSIS” - WILEY-VCH ED. J.F. HARTWIG "ORGANOTRANSITION METAL CHEMISTRY -UNIVERSITY SCIENCE BOOKS UPDATED REVIEWS FURNISHED BY THE TUTORS ON SPECIFIC SUBJECTS PRESENTED DURING THE SEMINARS.

	More Information
	LANGUAGE OF INSTRUCTION: ITALIAN ADDITIONAL INFORMATION: FURTHER INFORMATION CAN BE REQUESTED VIA E-MAIL: CPELLECCHIA@UNISA.IT

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Alfonso GRASSI | SUSTAINABLE CATALYSIS