Degradation of 2,4,6-trichlorphenol by producing hydrogen using

ultrasonic mist generated from photocatalysts suspension

1.Summary of the journal

Photocatalytic hydrogen production synergized with the oxidation of pollutants is an

environmentally friendly and economical approach to generate clean energy and
remove the pollution from environment. photocatalytic hydrogen production cooperating
with 2,4,6-trichlorophenol (2,4,6-TCP) degradation have been reinforced by introducing
an ultrasonic atomization. By introducing ultrasonic atomization, the atomized droplets
act as micro-photocatalytic units to replace the macrophotocatalytic reaction reactor.
The mass transfer distance for free radicals was therefore limited and the use of light
energy by photocatalysts increased. Therefore, the reliability of the response has been
enhanced. The results show the environmentally friendly and economic potential of
hydrogen production.

2. Objective of the journal

i. To investigate photocatalytic hydrogen production with ultrasonic atomization by

using different types of catalyst (mesoporous TiO2, g-C3N4 and mesoporous
Bi2O3), catalyst concentration, and ultrasonic atomization.

ii) To achieve the dual aims of pollution control and clean energy

iii) To to achieve the dual aims of pollution control and clean energy

3. Materials and methods (list all materials, methods and instruments)

Material: 2,4,6-trichlorophenol (2,4,6-TCP, 98%), melamine (99%), bismuth nitrate [Bi

(NO₃)₃.5H2O], nitric acid (HNO₃, 38%), sulfuric acid(H₂SO₄, 98%) ， triethanolamine
(TEOA, C₆H₁₅NO₃), absolute ethylalcohol (CH₃CH₂OH), chloroplatinic acid
(H₂PtCl₆.6H₂O), tetrabutyl
orthotianate (TBOT), titanium tetrachloride (TiCl₄), P123 (polyoxyethane-
polyoxypropane-polyoxyethane, blockpolyether, EO₂₀-PO₇₀-EO₂₀, MW =5800), cetyl
trimethylammonium bromide (CTMAB, C₁₆H₃₃(CH₃)₃NBr). All solutions were prepared
with deionized water throughout the experiments by a Milli-Q machine.

Methods: ultrasonic atomization method, hydrothermal method, acidizing stripping

method,

Instrument:
i. field emission scanning electron microscopy (FE-SEM, X650, Hitachi, JP).
ii. X-ray diffraction (XRD, X’Pert Pro MPD, PANalytical, NL) equipped with a Cu Ka
X-ray source.
iii. UV–vis absorption spectrum by a spectrophotometer (DR 6000, Hach; Loveland,
USA) in the wavelength range from 200 nm to 500 nm.
iv. diffusion reflection spectra (DRS) of samples by ultraviolet spectrophotometer
(Cary 500, Varian, USA).
v. Brunauer-Emmett-Teller (BET) surface area was measured on a Quantachrome
Autosorb-6B instrument (USA).

4. Choose 2 instruments

i. UV–vis absorption spectrum

ii. field emission scanning electron microscopy (FE-SEM)

5. Literature review

In this study, photocatalytic hydrogen production cooperating with 2,4,6-trichlorophenol

(2,4,6TCP) degradation have been reinforced by introducing an ultrasonic atomization
so the photocatalysts can achieve the dispersion of (mesoporous) photocatalyst which
can avoid the agglomeration of the particles. The degradation of 2,4,6-TCP in a mist of
three photocatalysts (g-C₃N₄, TiO₂, and Bi₂O₃) generated by ultrasonic atomization was
performed under 254 nm ultraviolet (UV254) light irradiation. The results showed that,
under UV254 irradiation, three different photocatalysts (g-C₃N₄, TiO₂, and Bi₂O₃) all
accelerated both hydrogen production and 2,4,6-TCP degradation. 2,4,6-TCP
degradation and photocatalytic hydrogen production showed a direct synergistic effect,
because 2,4,6-TCP has a strong propensity to react with photo-generated holes and
their second radicals in order to inhibit the recombination of the carrier and thus
increase the efficiency of hydrogen production at the same time. In addition, by
introducing ultrasonic atomization, the atomized droplets act as microphotocatalytic
units to replace the macrophotocatalytic reaction reactor.

The results reveal environmentally friendly and economical potential of hydrogen

production by photocatalytic degradation of 2,4,6-TCP in atomized droplets. with the
increase of catalyst concentration, the total hydrogen production immediately inhibited
might due to the agglomeration of photocatalyst particles and light shielding. The
proposed mechanism for hydrogen production by photocatalytic degradation of 2,4,6-
TCP in atomized droplets was proposed. We believe that the thin water film surrounding
the photocatalyst particles in the atomized droplet will shorten the pollutant and free
radicals transfer distance, and maximize the utilization of UV light, and sequentially
facilitate to the pollutant removal and the hydrogen production.

a. Basic theory or principle of the instrument

UV-Vis absorption spectrum

UV spectrophotometer principle follows the Beer-Lambert Law. This law states that
whenever a beam of monochromatic light is passed through a solution with an
absorbing substance, the decreasing rate of the radiation intensity along with the
thickness of the absorbing solution is actually proportional to the concentration of the
solution and the incident radiation. Based on the Beer-Lambert law, it has been
established that the greater the number of the molecules that are capable of absorbing
light at a certain wavelength, the greater the extent of the absorption of light.

Field emission scanning electron microscopy (FE-SEM)

A FESEM is microscope that works with electrons (particles with a negative charge)
instead of light. These electrons are liberated by a field emission source. The object is
scanned by electrons according to a zig-zag pattern. A FESEM is used to visualize very
small topographic details on the surface or entire or fractioned objects. Researchers in
biology, chemistry and physics apply this technique to observe structures that may be
as small as 1 nanometer. The FESEM may be employed for example to study
organelles and DNA material in cells, synthetical polymers, and coatings on microchips.
Electrons are liberated from a field emission source and accelerated in a high electrical
field gradient. Within the high vacuum column these so-called primary electrons are
focused and deflected by electronic lenses to produce a narrow scan beam that
bombards the object. As a results secondary electrons are emitted from each spot on
the object. The angle and velocity of these secondary electrons relates to the surface
structure of the object. A detector catches the secondary electrons and produces an
electronic signal. This signal is amplified and transformed to a video scan-image that
can be seen on a monitor or to a digital image that can be saved and processed further.

b. Applications of the instrument

UV-Vis absorption spectrum

Used for the detection of a functional group. It may be used to detect the absence or
presence of chromophore in a complex compound. It can also be used to measure the
degree of conjugation in polyenes. Other applications including for spectroscopic
titration, kinetic studies and studies of complex ion. UV spectroscopy can also help
determine the configurations of a geometrical isomer. It has been established that cis-
alkenes are absorbed at a different wavelength compared to trans-alkenes.
Field emission scanning electron microscopy (FE-SEM)

Applications of FESEM include:

 Semiconductor device cross section analyses for gate widths, gate oxides, film
thicknesses, and construction details
 Advanced coating thickness and structure uniformity determination
 Small contamination feature geometry and elemental composition measurement

c. Analyze the data

UV-vis is a traditional characteristics to analyze the absorptivity of semiconductor, and

then determine the band gap of the corresponding photocatalyst. The term “band gap”
represents the energy variation between the bottom of the conduction band to the top of
the valence band; electrons are capable of jumping from one band to another. For an
electron to jump from a valence band to a conduction band, it needs a band gap energy
which is a specific minimum quantity of energy for the transition. The diffuse reflection
(DR) is the radiation that penetrates into the powder sample and undergoes scattering
(it follows many reflections, refractions and diffraction at all directions due to
nanostructured mass) and wavelength dependent absorption within the
nanomaterial. The original idea to use the DR spectra recorded from
semiconducting nanostructures to calculate the Eᵍ was proposed by Kubelka-Munk
theory in 1931.Originally, the theory describes the behavior of light travelling inside a
light scattering sample. he Kubelka-Munk theory holds for a particle size that is
comparable or smaller than the wavelength of incident light and DR no longer permits
the secondary contributions of reflection, refraction, and diffraction. In the parabolic
band structure, the Eᵍ and absorption coefficient are related through the well known
Tauc plot. A Tauc plot is one method of determining the optical band gap in
semiconductors.

FESEM is the abbreviation of Field Emission Scanning Electron Microscope. A FESEM

is microscope that works with electrons (particles with a negative charge) instead of
light. FESEM can observe small structures (as small as 1 nanometer) on the surface of
cells and material. FESEM function by electrons which is released from the field
emission source and accelerated to a high electrical field gradient. Within the high-
vacuum column, these so-called primary electrons are oriented and deflected by
electronic lenses to produce a narrow scanning beam that bombs the object. As a
result, secondary electrons are emitted from every spot on the object. The angle and
velocity of these secondary electrons is related to the surface structure of the object.
The detector captures secondary electrons and produces an electronic signal. This
signal is amplified and transformed into a video scan image that can be viewed on a
monitor or a digital image that can be saved and processed further.