GENERATION OF HYDRATED ELECTRONS

THROUGH PHOTOREDOX CATALYSIS

GUIDED BY PRESENTED BY
Dr. MEERA V SHEEBA N K
ASSOCIATE PROFESSOR
TCR18CEEE15
GEC TRICHUR
 INTRODUCTION
 Water is one of the essential resource on our planet.

 Fresh water and the recycling of waste-water are very important topics in various areas.

 There are several ways to purifying water, from the old ways to the up-to date technology that we
have.

 The main objective of any water purification method is to produce safe and clean drinking water for
everyone.

 So depending on the purpose of water consumption, different methods for water purification were
established

 Photocatalysis based on nano‐catalysts is a very promising method for the treatment of contaminated
water.

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 INTRODUCTION
 Photocatalysis comprises a class of reactions which use a catalyst activated by light.

 There are two different types of photocatalytic applications in water treatment

1. Solar photocatalysis

2. Photocatalytic systems equipped with artificial ultraviolet (UV)‐light.

• Both systems can be applied at ambient temperature to degrade various chemical and microbiological

pollutants in water.

• Photoredox catalysis has emerged as a powerful tool for the utilization of visible light to drive chemical

reactions between organic molecules.

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 INTRODUCTION
 It is also a modern tool to generate reactive radical intermediates which avoids the use of traditionally

employed toxic and hazardous chemical reagents.

 Through photoredox catalytic reaction by suitable form of light source, the most reacting species

hydrated electrons can be generated.

 Hydrated electrons are the electrons moving freely in water that can degrade dissolved pollutants.

 These electrons are extremely reactive and can be used for a plethora of reactions.

 They break down even the most recalcitrant pollutants like chloroacetic acid, carbonyl compounds etc.

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 GENERATION OF HYDRATED
ELECTRONS
 The electrons have to be released from the molecular compounds in which they are usually tightly

bound.

 The easiest way to create a hydrated electron is to irradiate high power laser through water, which will

ionize water molecules and releases some free electrons.

 These electrons are surrounded by the water molecules from all sides, thus making them hydrated

electrons.

Hydrated electrons
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 PHOTOREDOX CATALYSIS METHOD

 Hydrated electrons can be generated in water through photoredox catalytic reaction with suitable form of

light source.

 Photoredox catalysts are often less toxic to generate free radicals.

 Photoredox catalysts are generally drawn from three classes of materials: transition-metal complexes,

organic dyes and semiconductors.

 Among this transition-metal complexes are commonly used as catalysts.

 The properties of photoredox catalysts can be modified by changing the ligands.

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 PHOTOREDOX CATALYSIS METHOD

 The photocatalytic system contains three processes

 Light absorption.

 MLCT (metal-to-ligand charge transfer) excited states.

 Quenching process.

Photoredox catalysis

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 PHOTOREDOX CATALYSIS METHOD
 Light absorption and MLCT excited states.

 Upon exposure to light, an electron of the metal ion is transferred from a dπ orbital of the metal to a

low-lying π* orbital of the bipyridyl ligand.

 The ground state of the photocatalyst is a singlet state (a state with no total electron spin) and a photon

absorption excites the catalyst to another singlet state of higher energy.

 This state is called MLCT state.

 In this state the catalyst can more readily give up one of its electrons or accept an electron from an

external source.
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 PHOTOREDOX CATALYSIS METHOD
 Quenching process

 The two most important quenching processes are energy transfer and electron transfer.

 The electron transfer process includes the oxidation or the reduction of the excited state.

 They are named as ‘oxidative quenching’ or ‘reductive quenching’.

 The term oxidative quenching and reductive quenching are used to describe two distinctive pathways,

 1. The reductive quencher reduces the excited state catalyst to the corresponding low oxidation state

species.

 2. And the oxidative quencher oxidizes the excited state catalyst to the corresponding high oxidation state

species. 9
 PHOTOREDOX CATALYSTS
 Ruthenium and iridium, especially tris-chelated complexes of Ru(II) with ligands 2,2′-bipyridyl and

1,10- phenanthroline are mostly used as photoredox catalysts.

 They are almost exclusively exploited and widely utilized in a variety of fields because of their

outstanding photophysical and chemical properties.

 These complexes will absorb energy from the visible region and give long lived, stable excited

states.

 The life time of excited state of [Ru(bpy)3]2+ is 1100 ns(nanosecond) .

 The life time of excited state of Ir(ppy)3 is 1600 ns.

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PHOTOREDOX CATALYSTS
RUTHENIUM COMPLEX

 Absorption at 452nm(visible light)

 Stable, long lived excited state

 Single electron transfer catalyst

 Effective excited state oxidant and

reductant.

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PHOTOREDOX CATALYSTS
IRIDIUM COMPLEX

 Max absorption at 375nm(visible light).

 Long lived excited state.

 Single electron transfer catalyst.

 Effective oxidant and reductant.

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 SACRIFICIAL DONOR
 Sacrificial donors are very important for photoredox reactions.

 They will provide an electron to the metals in its excited states.

 The two types of donors used are

 1. L-Ascorbic acid

 Commonly known as vitamin C which present in various foods, particularly of plant origin.

 2. Urate

 Urate is the conjugate acid of uric acid.

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 GENERAL MECHANISM FOR THE
GENERATION OF HYDRATED ELECTRONS
 The catalyst in its GS (ground state) absorbs a visible photon and shift to MLCT excited state.

 The lifetime of MLCT is 1 μs which is too short.

 The electron transfer from a sacrificial donor will convert the MLCT

in to OER (one electron reduced form).

 It is a stable state and act as first redox mediator.

 By adding another photon to eject an electron from OER the

GS recovered

 And the hydrated electrons formed act as second redox mediator

and attack the substrate. General mechanism

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 GENERATING HYDRATED ELECTRONS
WITH GREEN LED
 Hydrated electron generation has required complex and expensive high-power lasers.

 By using a green light-emitting diode as the sole energy source and Vitamin C and traces of a metal

complex as the catalyst the reaction can be carried out.

 Ruthenium-tris-bipyridyl ion [Ru(bpy)3]2+ is used as catalyst.

 Ascorbate dianion Asc2- is the sacrificial donor.

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MECHANISM INVOLVED
IN LED BASED REACTION
 Photons from the LED transform a ruthenium-based

photocatalyst into an excited state, with a central

oxidised ruthenium atom and a radical anion ligand. Micellar compartmentalization

 Vitamin C’s ascorbate dianion then quenches the excited species, producing a one-electron reduced
form of the complex

 Another photon can then eject the additional electron – generating the hydrated electron species
that can induce reduction reactions of organic compounds, and simultaneously returns the catalyst
to its ground state.
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 GENERATING HYDRATED ELECTRONS
WITH GREEN LED
 [Ru(bpy)3]2+/Asc2- system can provide synthetically useful amounts of hydrated electrons eaq˙− at 532

nm.

Radiant exposure vs hydrated electron generation

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 LIMITATIONS OF THE SYSTEM
 During the reaction, the catalysts had to be enclosed in tiny containers known as micelles like

SDS (Sodium dodecyl sulfate).

 The SDS effect is mainly due to the Coulombic repulsion between catalyst bearing micelles and

the sacrificial donor species.

 This will reduce the reactions efficiency and the micelle molecules themselves be partially

biodegradable

 The incorporation of products or reactants into the micelle will harm the catalyst and reduce the

efficiency of capturing hydrophilic hydrated electrons.

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 MICELLE FREE PHOTOREDOX
CATALYTIC SYSTEM
 By attaching carboxylate groups with bipyridyl ligands, the catalyst will retain its photophysical and

photochemical properties.

 By choosing the sacrificial donor as HUr2- the system not only suited a LED driven hydrated ion

source but also decreased the micellar environment.

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 MECHANISM OF THE REACTION

 Ruthenium polypyridyl complex in its GS absorbs a photon

and gives MLCT.

 The electron transfer from HUr2- makes it OER.

 Another visible photon will adds energy to eject an electron.

 The ejected electrons here is hydrated electrons and it will react

with pollutants.

• System works under 532 nm. Mechanism of generation

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 GENERATING HYDRATED ELECTRONS
BY AN INEXPENSIVE DIODE LASER
 Irsppy (Tris[2-phenylpyridinato-C2,N]iridium(III)) is a perfect water soluble compound which absorbs

below 500 nm and shift to the excited state of life time ∼1.6 μs.

 Thermodynamic considerations predict the photoionization (i.e., the light-driven release of eaq•−) of

excited Irsppy to be more favorable than that of excited ruthenium(tris)bipyridine [Ru(bpy)3]2+ by

∼0.6 eV.

 The ionization of [Ru(bpy)3]2+ requires highly energetic photons and Ir(ppy)3 requires only
inexpensive lasers.

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EXPERIMENTAL SETUP FOR HYDRATED
ELECTRON GENERATION
 1: Cw laser;

 2: Optics for collimation (either beam

expander or converging lens);

 3: Cuvette with stirring bar (and 3 mL of an

aqueous Irsppy solution);

 4: Water bath for cooling of illuminated

solution;

 5: Magnetic stirrer;
Experimental setup
 6: Beam block
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 GENERATING HYDRATED ELECTRONS
BY AN INEXPENSIVE DIODE LASER
 HAsc- is used as sacrificial donor.

 Blue continuous wave (cw) laser 447 nm is used for the generation of

hydrated electrons.

 Compared to other system that is able to produce eaq•−

this method is more efficient.

 Cw lasers do not suffer from the health and safety hazards connected

with pulsed lasers.

 Cost of experimental setup is less. Mechanism of generation

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 APPLICATIONS OF THE SYSTEM
 The catalytic system not only capable of,

 Detoxification of chloroacetate.

 Defluorination of 4-(trifluoromethyl)benzoate.

 Degradation of the benzyltrimethylammonium cation.

 Detoxification of chloroacetic acid

 NMR (Nuclear Magnetic Resonance) spectra, with identical vertical scales, before and after

illumination with a green LED (520 nm) for 27 hrs.

 50ƲM [Ru(bpy)3]2+ and 75mM Asc2- in 50mM aqueous SDS at pH 12.7) used to detoxificate 25mM

chloroacetate ClAc
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 APPLICATIONS OF THE SYSTEM

 The toxic ClAc is converted near-quantitatively

into the harmless acetate and Cl-, with

consumption of Asc2-

 Cl—CH2COO− + eaq˙− → Cl− + ˙CH2COO−

 CH2COO− + AscH− → CH3COO− + Asc˙−

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 APPLICATIONS OF HYDRATED ELECTRONS

 1. Treating Groundwater :

 Contacting the aqueous waste water or groundwater with an agent which generates hydrated electrons

on photolysis.

 Additionally, the aqueous waste water or groundwater is irradiated with UV light to photolyse the

hydrated electron generating agent, thereby generating hydrate electrons to degrade the contaminants.

 2. As one of the most reactive species, hydrated electron (eaq−) is promising for reductive

decomposition of recalcitrant organic pollutants, such as perfluorooctane sulfonate (PFOS).

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APPLICATIONS OF HYDRATED ELECTRONS

 3.The UV-254/sulfite-based ARPs(advanced reductive pathways) proved to be highly efficient

in producing hydrated elecrons which led to effective decomposition of BrO3 into Br-

 4. Chloroacetate pollutants can be eliminated in a small sample of water even when there was

only a moderate amount of sunshine.

 5. Hydrated electrons can be used for selective dechlorination of arenes, Carbonyl reduction

etc. under suitable conditions.

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 CONCLUSION
 Hydrated electron, which is listed among the most reactive species, has great potential for removal and

detoxification of recalcitrant contaminants.

 They are capable of reductively detoxifying chloro and fluoroorganics.

 Photoredox catalysis is a major approach for the generation of hydrated electrons.

 The method of generation of hydrated electrons by using visible light has been already invented.

 Instead of this LED can be used as the light source in the presence of vitamin C and traces of Ruthenium

metal complexes as catalysts.

 Iridium metal complexes has ideal properties to act as a photocatalyst for hydrated electron production

and this reaction requires only inexpensive diode laser as light source.

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 REFERENCES
 Bolton J R. and Cater R S. (2010): “Treatment of contaminated waste waters and groundwaters with
pholytically generated hydrated electrons”,vol.5,pp.125-130.

 Christopher K P., Rankic D A, and MacMillan W C. (2013): “Visible Light Photoredox Catalysis with
Transition Metal Complexes: Applications in Organic Synthesis”,vol,66.pp. 5322–5363

 Hart E J. (2011): “The significance of the hydrated electron in radiation chemistry”,vol.12,pp.641-651.

 Wang L., Rorich P., Ramanan P., Huang W., li R. and Zhang K. A. I. (2018): “Catalysis science and
technology”,vol.67,pp.789-810.

 Ikuta N., Zeng F. and Murata S. (2016): “Impact of substituents on Excited state and photosensitizing
properties in cationic Iridium(III) complexes with ligands”,vol.55,pp.8723-8735.

 Kerzig C., Guo X. and Wenger O S. (2018): “Unexpected Hydrated Electron Source for Preparative Visible-
Light Driven Photoredox Catalysis”,vol.141,pp.2122-2127.
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 REFERENCES
 Naumann R., Lehmann F. and Goez M. (2018): “Micellized tris(bipyridine)ruthenium catalysts affording
preparative amounts of hydrated electrons with a green light-emitting diode”,vol.24,pp.653-670.

 Lie A., Yumeng X. and Hong Y. (2012): “Synthetic applications of photoredox catalysis with visible
light”,vol.45,pp.354-359.

 Marchini M., Bergamini G., Cozzi P.G., Ceroni P. and Balzani V. (2017): “Phoredox catalysis:The need to
elucidate the photochemical mechanism”,vol.34,pp.537-5544.

 Naumann R., Lehmann F. and Goez M. (2017): “Generating hydrated electrons for chemical syntheses with a
green LED”,vol.57,pp.1078-1081.

 a. Naumann R. and Goez M. (2018): “A green-LED driven source of hydrated electrons characterized from
microseconds to hours and applied to cross couplings”,vol.39,pp.9833-9840.

 b. Naumann R. and Goez M. (2018): “First micelle-free photoredox catalytic access to hydrated electrons for
syntheses and remediations with a visible LED or even sunlight”,vol.26,pp.557-567 30
THANKYOU…

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