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Process development and DFT- optimization of the ZrV2o7

RANJNA CHOUDHARY AHIRWAR1*, Dr. RAJEEV DIXIT1, Dr .MANGLA DAVE GAUTAM1,

1. IPS/IES Indore-452012, India, Govt. Laxmibai pg college Department of Biochemistry Chemistry, Indore, 452001 India,

Govt Mata Jijabai pg college Department of Biochemistry indore-452001, India.

*Corresponding author: E-mail: [email protected]

A new type of nano crystalline vanadium inculcates zirconia material prepared by solution combustion method.

The material is characterized by x-ray diffractometer (XRD). The XRD studies revealed the material to be a

mixture of ZrV2O7 and ZrO2.

The effect of calcinations temperature on the phase transformation of the materials has been investigated by XRD

measurement. The material may be use for different type of oxidation and oxidative dehydrogenation reaction.

A-DFT and optimization has represent in this paper (zero point energy, Gibbs free energy electronic energy, IR

spectra of material surface contour, etc.)

INTRODUCTION There has been a considerable interest in the

development of more economical and eco – friendly

catalytic process for utility of alcohols to carbonyl or

ketones compounds because of utility of aldehyde

and ketones and acids in pharmaceuticals, dyes, and

perfumery and agro-chemical industries.

Traditional inorganic oxidants are costly, function in

halogenated inorganic solvents are environmental not

friendly. in the past years there has been a growing

demand for solid catalyst efficient in the partial

oxidation of alcohol for the production of fine and

stoichiometry inorganic reagents, though decreasing,

is still widespread. The present stringent ecological

standard increases the pressure to develop new,

environmentally benign methods. In many instances,

homogeneous catalysis provides powerful solutions,

but on an industrial scale the problems related to

corrosion and plating out on the reactor wall,

handling, recovery, and reuse of the catalyst represent

limitations of these processes.

Application of solid catalysts for the gas –or vapor

phase oxidation of simple, small-chain alcohols to the

corresponding carbonyl compound is well

established. An important requirement is the

reasonable and volatility and thermal stability of

reactant and product- a strong limitation in the

synthesis of complex molecule.

Solution combustion is a new process for rapid

synthesis of porous oxides, mixed oxides and

supported metal oxides. In this process, slurry

consisting of nitrates of the precursors is mixed with

a fuel like urea/citric acid and heated for few minutes

in a microwave oven till a solid gel is formed. The

gel is ignited in a muffle furnace to get the oxide

materials. To the best of our knowledge there is no

report on the mechanism of oxidation of benzyl

alcohol over ZrV2O7 catalyst employing any

quantum mechanical approach.

Density functional theory is the latest approach in

quantum mechanics to model reaction pathways and

transition states in chemical reactions. In the present

manuscript we report vapor phase air oxidation of

cyclohexanol over zirconium vanadate catalyst

prepared by solution combustion method with the

objectives of (1) optimizing the process conditions

for maximum yield to the ketones compound (2) to

model the transition states of the reaction by DFT

theory (3) to compute the activation energy of the

reaction and (4) to predict the mechanism of the

reaction.

Zr

o

v

o o

v

o

o

o

oo

o o

o

Fig: 1 structure of zirconium vanadate

Journal of Information and Computational Science

Volume 9 Issue 11 - 2019

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mailto:[email protected]

Catalyst preparation

ZrV2O7 catalyst was prepared by solution

combustion method. Salts of zirconium and

vanadium were used for the preparation of the

catalyst. Citric acid was used as a fuel. In a typical

preparation, 13.32 g of Zr (NO2), 0.6260 g of

NH4(VO3) and 27.92 g of citric acid were mixed in

minimum quantity of water to make a slurry. The

slurry was heated over a hot plate where it swells into

a gel. The resultant product was grinded and kept in

the muffle furnace for the calcinations at 600 °C for 4

h. After that calcined in different temperature like

600, 700 0 c for evolution of the yield of final

product. Yellow green product is obtained which is

further grinded in order to prepare a fine powder.

Computational methods Basic DFT calculations were performed using

Gaussian 09Wsuite19 and B3LYP functional. We

had used LANL effective core potential (ECP) with

double zeta potential (Lanl2dz) for optimization of

reactants, products, and transition state. This basis set

has overall combination of ECP and valence basis

set. The ECP parameters for vanadium atom have

been derived from atomic wave functions obtained by

all-electron on-relativistic Hartree–Fock calculations.

The light atoms (carbon, hydrogen and oxygen) were

optimized using 6-311G (d, p) basis set while for

heavy atoms (vanadium and titanium atom) we had

used lanl2dz basis set. Modeling of transition state

structure calculation QST2/QST3 keyword has been

used. At many places the optimization of transition

state was achieved directly also. Vibration

frequencies were calculated for the optimized

geometries to identify the nature of the reactant or

product (no imaginary frequency) and TS structure

(one imaginary frequency). RB3LYP was used for

singlets and UB3LYP for higher multiplicities. In

UB3LYPcalculations separate a and b orbital’s are

computed. The calculation for singlet diradical

system has been performed using “guess ¼(mix,

always, density mix)” keywords. This keyword helps

to predict atomic spin density (Unpaired electron

density), if alpha and beta electron densities were

situated over different atoms i.e. singlet diradical

system. We had also calculated the “open shell vs.

closed shell correction term” over 6-311G (d, p) basis

set as it includes all electron calculation. This term is

used to eliminate the error which may arise due to

closed shell calculations.

The enthalpy and the activation energies were

calculated at the reaction temperature as described by

J. W. Ochterski.

The Adsorption energy (Eads) was calculated

Eads= E (adsorbate_-substrate)_ (EAdsorbate + Substrate).

The chemical reactivity of various oxygen atoms has

been described in the form of Fukui functions. We

have also calculated

the Fukui functions for the different type of oxygen

atoms present in our catalyst.

Enthalpies and free energies of reaction Enthalpy of reaction can be calculated by-

ΔrH0(298K) =Ʃ product ΔfH0(298K)- Ʃ rectant

ΔfH0(298K)

ΔrH0 (298K) = Ʃ (ε0+Hcorr) product

Ʃ (ε0+Hcorr) reactant

Where, ε0= electronic energy, Hcorr= thermal energy, Gcorr= Gibbs free energy correction Gibbs free energy of reaction can be calculated

by

ΔrH0(298K) =Ʃ product ΔfH0(298K)- Ʃ rectant

ΔfH0(298K)

ΔrH0 (298K) = Ʃ (ε0+Gcorr)product

Ʃ (ε0+Gcorr) reactant

Where, ε0= electronic energy, Hcorr= thermal energy, Gcorr= Gibbs free energy correction



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Detection method:

Catalyst was characterized by X-ray diffraction

(XRD) and Raman analysis. XRD in the 2θ range 0-

90° was performed over Rigaku X-ray powder

diffractometer equipped with graphite-crystal

monochromator employing CuKα radiation of

wavelength 1.5406 Å as a source. The average particle

size was calculated from (111) diffraction peak using

Scherer’s equation:

D = 0.9/ (cos )

Where D is the average crystallite size in nm, λ is the

wavelength of source X-ray (0.154 nm), β (in

radian) is the full peak width at half maximum.

Raman spectrum of the sample in the range 50-4000

cm-1 was recorded over a Labram HR800 micro

Raman spectrometer using Lab spec software. An

Ar+ source with the wavelength 2.53 eV was used as

a source.

The product containing reaction mixture was

analyzed with the help of a chemito1000

Chromatograph using SE-30 column and FID

detector.

X-ray diffraction analysis: Powder XRD

pattern of the prepared nanoparticles was recorded in

order to explore structural features of zirconium

supported mesoporous vanadium materials. Fig.

depicts XRD patterns, which confirms that the

vanadium ions have occupied the zirconium ions at

their lattice positions with high dispersion of

vanadium ions on zirconium oxide surface. A sharp

peak appeared at 26.30°, which can be ascribed to

tetragonal phase of ZrO2. The average particle size was

calculated from (111) diffraction peak using Scherer’s

equation. The average particle size found within the

range of 20-30nm.

Fig 2: XRD pattern of Zrv2o7 at ( 6000C)

20 30 40 50 60 70 80

100

200

300

400

500

600

700

800

nte

nsity

2 theta



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Raman analysis and SEM The bands appeared at 125.1, 213.6 and 307.2 cm-1 is assigned to ZrO2. The low frequency bands

appeared at 125.1, 213.6 are assigned to lattice vibrations. Bands appeared at 524.2 cm-1 can be

attributed to bending modes of water. The band appeared at 702 cm-1 in the Raman spectrum can be

ascribed to stretching vibration of short V=O bond. A strong Raman band at 674.2 cm-1 is generally

assigned to V=O stretching mode of bulk V2O5 [39]. Weak intensity of this band in the present recording

suggests low concentration of bulk V2O5 (Fig. 2).

0 300 600 900

0

200

400

600

NT

EN

SIT

Y

RAMAN SHIFT

% (intensity)

125.1

213.6 307.2 524.2 674.2

0 2 4 6 8 10

0

2

4

6

8

10

2000 3000 4000

1.00

1.01

1.02

1.03

TR

AN

SM

ITT

AN

CE

%

WAVENUMBER CM-1

2361

.49

3743

.07 38

28.6

2

Fig: 3 Raman and FT-IR spectrums of the ZrV2O7 nanoparticles



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Fig: 4 SEM Images of catalyst



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A Bond order B

Bond length

C

Mullikan charge

Fig 5: Optimization of ZrV2O7 (A) Bond length (B) Bond order (C) Mullikan charge

OPTIMIZATION

Optimization gives us the result in the form of summery of catalyst. With the help of this summery we get the

different energy value. The enthalpy and the activation energies were calculated at the reaction temperature as

described by J. W. Ochterski. [34]

The Adsorption energy (Eads) was calculated

Eads= E (adsorbate_-substrate) _ (EAdsorbate + Substrate).



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(A)

(C)

(B)



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Fig: 6 (A) IR Spectra of vanadate, (B) optimized vanadate (c) spectra of total energy RMS gradient of catalyst.

Overview Tab Data Section:

Vanadate new 1.1

C:/g16w/vanadate.chk

File Type = .chk

Calculation Type = FREQ

Calculation Method = RHF

Basis Set = STO-3G

Charge = 0

Spin = Singlet

Solvation = scrf=check

Electronic Energy = -6261.2429 Hartree

RMS Gradient Norm = 9.4492344e-06

Hartree/Bohr

Imaginary Freq =

Dipole Moment = 7.5878331 Debye

Polarizability = 76.096603 a.u.

Hyper Polarizability = 174.40893 a.u.

Fig: 7 Surface and contours 0 state

Fig: 8 - 0.02 multiple surface of catalyst homo lumo0.02 multiple surface of catalyst homo lumo



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Fig 9: Optimization step number graph of vanadate.



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CONCLUSION

This work demonstrates the synthesis of mesoporous

or nanoporous ZVX materials by solution

combustion method.

The study of XRD patterns of the majority of

monoclinic phase of ZrO2 at higher temperature. We

had also present in this paper the density functional

theory of zirconium vanadate, the vanadate present

0.02 multiple surface of catalyst homo lumo0.02

multiple surface of catalyst homo lumo surface homo

and Lumo Surface and contours.

Optimization of zirconium vanadate which give us IR

spectra of catalyst which indicates optimization step

number and RMS gradient of total energy.

Dipole Moment = 7.5878331 Debye

Polarizability = 76.096603 a.u.

HyperPolarizability=174.40893a.u.

The equation determination which used for

computing thermochemical n data in gaussian are

equivalent in standard texts on thermodynamics.

Most important approximation to be aware of

throuout this analysis is that all the equation assume

non- interacting particles and therefore apply only to

an ideal gas. The complete analysis based on purity

by characterized by XRD and FT-IR and SEM

Images of vanadate.

.

Acknowledgments

The authors are thankful to UGC-DAE-CSR, Indore, India for XRD analysis. The authors are also grateful to IPCA

Laboratories, Indore, India for GLC recordings AND Dr. Hari Singh Gour Sagar Central University for FT-IR-

Raman Spectroscopy analysis.



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