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Introduction .................................................

Current uses of TiO2 Photocatalysis .............4

Application of TiO2 Photocatalysis ...............6

Figure I ........................................................8

Figure II .......................................................9

References ...................................................10

Photocatalysis

Introduction

The definition of photocatalysis is basically the acceleration of a photoreaction by the


presence of a catalyst. A more in depth approach would include that the catalyst may
accelerate the photoreaction by interaction with the substrate in its ground or excited state
and/or with a primary photoproduct, depending upon the mechanism of the photoreaction
[1].

Catalysis by definition, implicates a catalytic entity that participates and accelerates the
chemical transformation of a substrate, itself remaining unaltered at the end of each
catalytic cycle [1]. In photocatalysis, no energy is stored; there is merely an acceleration
of a slow event by a photon- assisted process.

It would probably be a good time to introduce a few of the many ways in which
photocatalysis works in basic easy to understand terms. In figure one; M is the metal
containing catalyst or catalyst precursor, O is the organic reactant, P is the product, C’ is
the photoassistor also pseudocatalyst, R is the primary photoproduct, and hv is the
irradiation via ultraviolet or visible light. The simplest most basic equation is that the
irradiated subject is changed to an excited state thus increasing the ease of bond making
and braking which ultimately renders the organic reactant to a desired product. As
previously mentioned figure one includes schemes 5-9. Scheme 5 illustrates the process,
commonly termed photosensitization, in which the interaction between electronically
excited M and ground-state substrate activates the latter and regenerates M. In scheme 6
the reaction of M* (the exited M) produces a ground state species, C’, which assists the
transformation of substrate to product and then reverts to M. Scheme 7 describes the case
in which M catalyzes the reaction of an electronically excited organic substrate via
formation of an excited complex, M-O*. Scheme 8 involves a metal-catalyzed reaction of
a primary photoproduct, R. Lastly, Scheme 9 illustrates a transformation that results from
irradiation of a ground state M-O complex [1].

Machines or specially designed equipment are needed in this field because


inconveniences and detrimental factors in direct solar photolysis are the lack of sunlight
absorption by the substrates, attenuation of the sunlight, and the relatively shallow
penetration depth of sunlight in natural aquatic bodies.

There are many types of catalyst, some act on very few substrates while some act on
many substrates. The best way to cleanse a wastewater would be to use a photocatalysis
process that can be effective on a multitude of contaminants or in other words a
heterogeneous environment of contaminants. Metal oxides work well in this case. It is
true that many oxides work well, WO3, and ZnO but in scientific studies it has been
proven that TiO2 has an advantage over the others.

The reasons that TiO2 does so well and is desired as an agent in remediation of
wastewater is based on several factors. 1. The process occurs under ambient conditions.
2. The formation of photocyclized intermediate products, unlike direct photolysis
techniques, is avoided. 3. Oxidation of the substrates to CO2 is complete. 4. The
photocatalyst is inexpensive and has a high turnover. 5. TiO2 can be supported on suitable
reactor substrates. 6. The process offers great potential as an industrial technology to
detoxify wastewaters [1].

Current Uses of TiO2 Photocatalysis

Researchers have used photocatalytic oxidation (PCO) to break down and destroy many
types of organic pollutants. It has been used to purify drinking water, destroy bacteria and
viruses, remove metals from waste streams, and breakdown organics into simpler
components of water and CO2.

After photocatalysis was realized to be a great oxidation mechanism, researchers began


testing it on many different compounds, and in many different processes. To date, this
technology has been used to detoxify drinking water, decontaminate industrial
wastewater, and purify air streams.

Photocatalytic Treatment of Water


Some of the first experiments showed that chlorinated aliphatic hydrocarbons were
dechlorinated and mineralized [2]. This means that the compounds were broken down
into water and CO2. Before long researchers realized that this advanced oxidation
technique could be used on many compounds, including some aromatics that are resistant
to normal oxidation reactions [2]. According to Purifics, an industrial water treatment
company specializing in photocatalysis, many different chemicals have proven to be
detoxified or removed from water [3]. These chemicals include:

Organic Families Toxic Compounds

alkanes PCB’s

alkenes PAH’s

alkynes dioxins

ethers furans

aldehydes pesticides

ketones herbicides

alcohols phenols

amine compounds cyanide

amide compounds

esters

Treatment of water can be accomplished by adding a powdered form of TiO2 to the water,
or it can be immobilized on a substrate. If TiO2 is in solution then some sort of recovery
system is necessary in order to reuse the catalyst.

Photocatalysis has not only been proven to remove pollutants from water, but also
nuisance color, taste and odor compounds [4]. Tests have also proven TiO2 to effectively
remove bacteria, and viruses from water supplies. A study by Ireland et. al. showed that
TiO2 oxidation effectively removed Escheria coli (E. coli) from drinking water [5].

Photocatalytic Treatment of Air

Treatment of polluted air streams is often more efficient that treating liquid waste
streams. Gas phase kinetics allow reactions to occur much faster than in the liquid phase.
This fact has lead some people to utilize air stripping of pollutants from liquid phase for
treatment in the gas phase. In the process of treating air streams, TiO2 must be suspended
on some sort of surface to allow the gas to pass over it and react. This is usually some
sort of matrix with a high surface area, which the UV light is shown upon.

An air treatment system for ethylene removal has been developed at University of
Wisconsin-Madison [6]. This system will be placed in produce sections of grocery stores
to remove the naturally occurring ethylene that causes fruits and vegetables to spoil. The
UV light has also shown to reduce bacteria, molds and odors [6].

Application of TiO2 Photocatalysis

A common application for TiO2 photocatalysis is the mineralization of trichlorotmehtane


(CHCl3). Trichloromethane is a suspected carcinogenic chloroform produced from
dissolved organic matter during conventional water chlorination procedures[2]. This
purification process is shown to be very effective in an experiment performed by David
F. Ollis, a chemical engineer at North Carolina University. According to his results
published in Environmental Science and Technology, "The simultaneous presence of
illumination and TiO2 produced the chloride ion and caused the disappearance of
chloroform" [2]. The basic general equation for chloroform breakdown is given below:

H2O + CHCl3 + (1/2)O2 => CO2 + 3HCl

The oxygen needed for the experiment is aerated throughout the contaminated water. The
statement given states that a chloride ion is produced. Figure II shows that the ions
combine with hydrogen to form a more desirable compound HCl [2]. Ollis’ experiment
shows great promise and provides ample information to show its success. Figure II also
shows the differences in using only one of the procedures at a time compared to using
both procedures at the same time. The results are staggering showing a combined effort
associated with a drastic drop in tricholormethane. Overall the experiment is well
documented and explained. One problem addressed when using the insoluble catalyst
TiO2 is the need to recover and reuse this material. After much research, we would
suggest experimenting with immobilizing the catalyst perhaps placing TiO2 in glass.
Immobilizing the catalyst can cause a wide range of problems from lower efficiency to
difficulties in mass transport, but that is beyond the scope of the paper.