Method development for in situ monitoring of mechanochemical reactions by Raman spectroscopy and powder X–ray diffraction

doctoral thesis

• Title (croatian): Razvoj metoda za praćenje in situ mehanokemijske sinteze Ramanovom spektroskopijom i difrakcijom na praškastom uzorku
• Author: Stipe Lukin
• Mentor: Ivan Halasz (mentor)
• Committee member: Ivica Đilović (predsjednik povjerenstva)
• Committee member: Carsten Bolm https://orcid.org/0000-0001-9415-9917 (član povjerenstva)
• Committee member: Darko Babić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2019-09-30, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

Milling reactions are conducted in high-energy ball mills in a closed assembly comprising of
a milling jar, sample, and a milling media. So far, monitoring a reaction course of such
reactions required periodic disruption of the milling process and sampling for further ex situ
analysis. Thus, information obtained in that way might not reflect the true nature of milling
reactions. Recently introduced in situ approach based on synchrotron powder X-ray
diffraction and Raman spectroscopy for monitoring milling reactions have been superior to
the already established ex situ analysis. This thesis represents a further development of
methods for uninterrupted real-time and in situ monitoring of milling reactions. Here, a detail
description of experimental setup and data analysis is given, and developed methods were
used for studying solid-state synthesis of metal-organic frameworks ZIF-6 and ZIF-8,
Knoevenagel condensation between barbituric acid and vanillin, isotope-exchange reactions
between benzoic acid and deuterated water, 2-pyridone, or paracetamol, and finally,
competitive cocrystallization reactions between nicotinamide and benzoic, anthranilic, or
salicylic acid.

Abstract (croatian)

Reakcije mljevenjem odvijaju se u specijaliziranim mlinovima unutar zatvorenih posuda u
kojima se nalaze reaktanti i kuglice. Praćenje takvih reakcija je zahtjevalo periodičko
zaustavljanje mljevenja i uzorkovanje reakcijske smjese za daljnu anlizu ex situ. Stoga,
informacije dobivene na ovaj način ne moraju nužno odgovarati stvarnim kemijskim i
fizikalnim procesima koji se odvijaju tijekom reakcije. Nedavno uvedene metode praćenja
reakcija mljevenja, temeljene na difrakciji na praškastom uzorku i Ramanovoj spektroskopiji
in situ, pokazale su se superiornim u usporedbi s dosad korištenim metodama ex situ. U ovoj
disertaciji prikazan je daljnji razvoj metoda za neprekidno praćenje reakcija mljevenja, te je
dan detaljan opis eksperimentalnog postava i obrade prikupljenih podataka. Razvijene
metode iskorištene su u proučavanju sinteze u čvrstom stanju metalo-organskih mreža ZIF-6 i
ZIF-8, Knoevenagelovoj kondenzaciji između barbiturne kiseline i vanilina, reakcijama
izmjene izotopa između benzojeve kiseline i deuterirane vode, 2-piridona ili paracetamola, i
kompetitivnim reakcijama kokristalizacije između nikotinamida i benzojeve, antranilne ili
salicilne kiseline.

• Keywords: in situ; monitoring; mechanochemistry; PXRD; Raman; solid state
• Keywords (croatian): in situ; mehanokemija; čvrsto stanje; Raman
• Language: english
• URN:NBN: urn:nbn:hr:217:083226
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 251 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2021-10-01
• Created on: 2019-12-05 13:17:36