Material Katalis dan Fotokatalis (MKF)

Material Katalis Material Fotokatalis

SILABI MATERIAL KATALIS DAN FOTOKATALIS ( MKF )

1. Sejarah dan Perkembangan Material Katalis 2. Konsep Dasar Reaksi Katalisasi 3. Material Katalis Homogen dan Heterogen : Reaksi, Desain Sintesis, Karakterisasi dan Uji Unjuk Kerja Katalis 4. Sejarah dan Perkembangan Material Fotokatalis 5. Sintesis dan Karakterisasi Material Fotokatalis 6. Aplikasi Material Fotoaktif : Fotokatalisasi oksidasi dan reduksi serta Unjuk kerja, Fotokatalis dalam sistem Fotovoltaik dan Unjuk Kerja 7. Perkembangan terkini sintesis material fotokatalis : material responsif cahaya tampak, material core-shell, material nanostruktur (nanorod,nanotube,nanowire)

Prasyarat : KIMIA DASAR

Dosen Pengasuh :

SEMESTER GENAP

Prof Dr Wega Trisunaryati Dr Indriana Kartini Dr. Akhmad S

HETEROGENEOUS CATALYSTS
Solid catalyst Photocatalysis by semiconductor materials

 A CATALYST is a substance that increases the rate at which a chemical reaction approaches equilibrium, while not being consumed in the process kinetic aspect catalyst provides alternative reaction mechanism of lower activation energy materials used: insoluble, nonvolatile solid as catalyst important properties:
activity selectivity

advantages of using solid catalyst in a fluid-phase reaction heterogeneous catalyst :

minimal lost of the catalyst minimal contamination of the reaction products stay physically in place of the reaction chambers

Heterogeneous catalysis of a reaction between two molecules can occur only when both molecules are adsorbed on to a solid surface

Photocatalysis
CO2 + H2O CO2 Chlorophyll

Photocatalyst Organic Compound H2O Starch + O2 Organic compound + H2O + O2

Photocatalytic Applications

Antimicrobial Effect

Antimicrobial Effect

Self-Cleaning Effect

When water hit surfaces

Water beads Water spreads

Hydrophilic surface =wetting

Hydrophobic surface = beading

Contact angle differences

Poor wetting (beading) Contact angle > 90 Good wetting Contact angle < 90

Contact angles below 90 indicate good wetting, while contact angles above 90 indicate poor wetting (beading).

THE LOTUS LEAF EFFECT

The leaves of Lotus plants have the unique ability to avoid getting dirty.They are coated with wax crystals around 1 nanometre in diameter and have a special rough surface. Droplets falling onto the leaves form beads and roll off taking dirt with them, meaning the leaves are selfcleaning. Sometimes referred to as The Lotus Leaf effect

SELF CLEANING GLASS

Scientists have mimicked nature at the nanoscale to create glass surfaces that are self-cleaning like the Lotus leaf.

Self cleaning glass

Normal glass

No more scrubbing of shower screens!

No more Spiderman window cleaner!

SELF CLEANING GLASS

HOW DOES IT WORK?
Glass is coated with a layer of nanocrystalline titanium dioxide (TiO2). The titanium dioxide reacts to the ultraviolet (UV) component of sunlight causing a gradual break down and loosening of dirt. This is known as the photocatalytic stage.

SELF CLEANING GLASS

HOW DOES IT WORK?
The reaction also causes the glass surface to become super hydrophilic. This forces water to spread across the surface like a sheet, rather than beading, thereby washing away the loosened debris on the surface of The glass as it falls. This is the hydrophilic stage.

SELF CLEANING GLASS

HOW DOES IT WORK?
Another type of self cleaning glass uses hydrophobicity, not hydrophilicity. This type of glass is given a coating which makes it super hydrophobic, meaning water forms beads and runs of the glass. This type of glass is used indoors, such as in shower screens, where there is no sunlight enable use of the other type of glass.

Photocatalysts

Band Gap Positions in Various Semiconductors

eV
0

Vacuum level

E vs. NHE

-3.0

Lower edge position of CB

-1.0

-4.5

1.1

-4.0

2.3

3.0

0 H+/H2

1.7

-5.0

Si 2.8 3.4 3.4 3.2 2.8 3.2 3.2 5.0 3.8

-6.0

2.5
+1.0

3.0

2.7

2.2

3.2

O2/H+
GaP SiC CdSe CdS
+2.0

-7.0

Fe2O3
-8.0

+3.0

MnTiO3 TiO2 TiO2SrTiO3 FeTiO3 BaTiO3 Rutile Anatase

KTaO3 Nb2O5 WO3 ZrO2

ZnO2

Upper edge position of VB

SnO2 @ pH = 0

Mechanism of photocatalysis

e-

CB

hv
surface recombination

h
B+
+ + OH , R+

h+

VB

+ +
AO2-, H2O2

++

Volume recombination

photogenerated hole highly oxidizing

O2

B
H2O2, OH-, R

Why TiO2?
Good photoactivity (band gap=3.2ev) oxidation of most VOC & water (Strong oxidizing power) High Photo & chemical stability, non-toxicity Low cost, ease of availability, can be reused Photocatalysis takes place at ambient temperature Atmospheric oxygen is used for the reaction

Photocatalysis goes to TiO2 era

1 n-type TiO2 electrode 2 platinum black counter electrode

3 ionically conducting separator

5 load resistance

4 gas buret
6 voltmeter

Fujishima A.Honda K.,Nature197237(1):238-245.

Redox potential of
1.

+ h

The redox potential for photogenerated h+ is +2.53 V vs. the

SHE
2. 3. After reaction with water, these h+ can produce OH Both h+ and OH are more positive compare to ozone

Introduction: Photocatalytic Process

TiO2 hv e- + h+ h+ + H2O OH + H+ e- + O2 O2- O2- + H+ HO2 TOC + Ox TOC (partially oxidized species) + CO2 + H2O

Photo-generation electron/hole pairs Formation of radicals

Radical oxidation of organic compound.

Photocatalytic Reactions
TiO2 + h h+ + H2O O2 + eO2 - + H+ HO2 + HO2 O2
-

TiO2 (e- + h+) OH + H+ O2

-

HO2 H2O2 + O2 O2 + HO2H2O2 2 OH HO + OH- + O2 HO + OH-

+ HO2

HO2- + H2O2 + h H2O2 + O2

-

H2O2 + e-

Entail Physicochemical Properties of TiO2

The applications of TiO2 is a function of specific physicochemical properties like: High Surface area Small Crystalline Size Anatase form of TiO2 High crystallinity Porous structure Activation light source

Challenge of TiO2!!!
Because TiO2 has a high band gap (~ 3.2 eV), it is excited only by UV light ( <388 nm) to inject electrons into the conduction band. Thus, this limits the use of sunlight (3~5%) or visible light as an irradiation source in photocatalytic reactions on TiO2 .
In addition, the high rate of electronhole recombination on TiO2 particles results in a low efficiency of photocatalysis

next will be on: fundamental concepts for photocatalyst material