PHOTO CATALYTIC FIXATION OF

DINITROGEN

Ph.D. Seminar I
G. Magesh
9-5-06

Contents
Importance of fixation of dinitrogen
Properties of dinitrogen
Various methods for fixation of dinitrogen
Shortcomings in available methods
Merits of photo catalytic fixation of dinitrogen
Fundamentals of photo catalysis
Challenges in photo catalytic route
Ways of overcoming them

Importance of fixation of dinitrogen

Nitrogen - necessary for functioning of biomolecules and plant

growth

Important component of fertilizers and medicines

Present in dyes, explosives and resins

Ammonia - starting material for nitrogen containing chemicals

Usage of ammonia in various industries

Nitrogen cycle

Various processes involved in nitrogen cycle

Encyclopaedia Britannica, Encyclopaedia Britannica (1998)

Sources of fixed nitrogen

Haber process
Fixed nitrogen by bacteria and algae
Chile salt petre (Sodium nitrate)
Destructive distillation of decayed vegetable and animal matter
Reduction of nitrous acid and nitrites with nascent hydrogen
Decomposition of ammonium salts by alkaline hydroxides or quicklime
Mg3N2

6 H2O

3 Mg(OH)2 + 2 NH3

Fixed nitrogen before and after Haber process

Fixed Nitrogen Production (1000 tons)

1913

1934

World

843.5

1972.0

Chile

476.7 (56.5%)

141.8 (7.2%)

Germany

131.6

462.5

Great Britain

99.5

175.0

United States

39.5

256.7

Norway

22.0

65.5

France

18.9

187.6

Canada

12.7

41.1

Belgium

11.0

109.8

Italy

6.3

98.6

Japan

3.9

208.0

Russia

3.2

45.0

Properties of dinitrogen which makes it inert

Dinitrogen - two N atoms connected by triple bond

Breaking the NN bond is difficult - high dissociation energy of 942 kJ mol-1

Breaking first bond requires 540 kJ mol-1

Very weak base no interaction with even strong acids

Non-polar

Initial hydrogenation is highly endothermic for N 2

N 2 + H2

N 2 H2

H = 213.5 kJ mol-1

2 C + H2

C2H2

H = -175.8 kJ mol-1

Other important properties

Gas

Nitrogen

Carbon

Oxygen

Argon

Ionization potential (eV)

14.3

11.256

13.614

15.755

Electron affinity (eV)

0.073

1.595

1.461

Solubility in water (mole/cm3)

0.083

Insoluble

0.153

0.140

Property

High ionization potential and low electron affinity - difficult to reduce and
oxidize
Solubility very less - reactions in solution phase - difficult

Activation of dinitrogen

LUMO

22.9 eV
HOMO

Molecular orbitals diagram of N2 molecule

Very difficult to activate dinitrogen using light, heat and potential

HOMO very low w.r.to e- acceptors
LUMO very high w.r.to e- donors
T.A.Bazhenova and A.E.Shilov, Coord. Chem. Rev. 144 (1995) 69-145

Stepwise redox potentials

Redox potential dependence on the number of electrons transferred

Initial two electron transfer requires higher potential

NH3 formation - six electron process - less probable

Chatt J, Camara L M P, Richards R L, New Trends in the Chemistry of Nitrogen Fixation,

10
Academic Press, (1980)

Thermodynamics of fixation of N2 to ammonia

N2 + 3H2

2NH3

H= -36 kJ mol-1

Change in entropy, S = - ve
II law of thermodynamics - Natural processes tend to increase the entropy
Formation of ammonia by this route cannot be a natural process
Spontaneous reaction G = ve
G negative at very low temperatures

11

Available methods of fixing dinitrogen

Haber process

Fe based catalyst

N2 + 3H2

400C, 200 atm

2NH3

Water gas shift reaction

Various steps in Haber process

12

Limitations with the Haber process

Forward reaction - reduction in number of molecules

Le Chatelier principle - high pressure forward reaction

Not desired in industries - accidents and increased cost

Forward reaction - exothermic

Temperature must be minimum - Le Chatelier principle

To achieve high rates in industries - temperature at 400C

Conversion of 15%

Hydrogen
Obtained from fossil fuels a limited resource
Production requires major part of plant and cost
Releases green house gases like CO2 and CO

13

Biological fixation of dinitrogen

Enzyme nitrogenase

Present in soil bacteria, root nodules and algae

Two decades of research - mechanism not established

Enzyme contains Mo and Fe

Proposed mechanism - complexation of N2 to metal ions

Reduces bond strength - breaking 1st bond easier

Limitations with biological route:

Nitrogenase - sensitive to O2 requires O2 free environment
Sensitive to environmental conditions - temperature, pH
Cannot be used for large scale N2 fixation

14

Fixation of dinitrogen by metal-nitrogen complexes

Fe, Ti, Zr, Mo - high affinity for N2
Electron rich ligands TMS, phosphine
Perturbing N2 donates e- to LUMO of N2
Compound

N-N bond
length(
)

Structure of

N2 gas

1.0975

[(TMS2N)2Ti]2-(N2)2-

H2NNH2

1.460

complex

[(TMS2N)2Ti]2-(N2)2-

1.379

Limitation:
N2 evolution during reduction
Fryzeuk M D, Johnson S A, Coord. Chem. Rev., 200 (2000) 379

15

Alternatives
Haber process

Dissociative adsorption of N2 High temperature and pressure

Metal complex based reduction

Binding N2 Perturb e-

acceptor orbital (wave function)

e- donation LUMO of N2

Limited success

Look for
Perturb orbital (wave function) of e- donor and acceptor
e- donation to LUMO N2 activation

Very strong N2 adsorption

Hydrogen addition without interruption

16

Merits of photo catalytic fixation of dinitrogen

Utilizes light and efforts are on to use sunlight - a renewable source

H2 for reduction obtained from water - a widely available source

No pollution associated with the process

Process of photo catalysis is well understood

Carried out at atmospheric pressure and room temperatures

Methods to perturb catalyst orbitals transfer e- to LUMO

17

Photo catalysis
Photo catalysis - reaction assisted by photons in the presence of a catalyst
In photo catalysis - simultaneous oxidation and reduction
Light excites electrons from valence to conduction band - electrons and
holes

Light induced excitation processes in a photo catalyst

18

Choice of materials as photo catalyst

Choices Metals, semiconductors, insulators
Catalyst - absorb light in UV or visible region - easily available

CB

Metal

CB

No band gap
Only reduction or oxidation band
position

Semiconductor

Optimum band gap

UV or Visible light

Insulator

High band gap

Requires light - higher energy than UV

light

CB

VB
Metal

E
n
e
r
g
y

VB
Semiconductor
VB
Insulator
Band gap of available
materials

19

Types of semiconductors
For reduction
Conduction band potential - more negative than potential of reduction reaction

For oxidation
Valence band potential - more positive than potential of oxidation reaction
-ve
P

OR Type Oxidation and Reduction o

R Type

Reduction

O Type

Oxidation

X type

- None

t
e
n
t
i
a
l

Reduction (A / A-)

Oxidation (D/D+)

+ve
Band positions of various types of semiconductors

20

E
n
e
r
g
y

Requirements of photo catalyst for fixation of N2

N2/NH3 = + 0.059 eV
H+/H2 = 0.000 eV
Conduction band potential - more
negative than above potentials
H2O/O2 = 1.229 eV

N2/NH3

eV

Valence band potential - more positive

than above potential
Very strong N2 adsorption
No photocorrosion

Band positions of semiconductors w.r.to reactions

Good light absorption

Chemically inert

21

Photocorrosion
CdS, ZnS, ZnO undergo
photocorrosion
Activity decrease as the time increases
Catalyst gets oxidised
Oxidation potential of catalyst More
-ve than desired oxidation reaction
potential
S deposition on catalyst - reduce
light absorption

Oxidation potentials of catalysts w.r.to

band positions

h+ = hole

22

Selection criterion for dopant ions in semiconductor

Doping cations and anions altering band positions
Increase in ionic character of M-X bond - band gap decreases and vice versa
% Ionic Character = ( 1 - exp [- (X M - XX)2 / 4] ) x 100
Semiconductor

M-X

Percentage
ionic
character

TiO2

Ti-O
Ti-O-Sr
Fe-O
Zn-O
W-O
Zn-S
Cd-S
Cd-Se

59.5
68.5
47.3
55.5
57.5
18.0
17.6
16.5

SrTiO3
Fe2O3
ZnO
WO3
ZnS
CdS
CdSe

Viswanathan B, Bull. Catal. Soc. India, 2 (2003) 71

X- electronegativity

23

Photo catalytic fixation of dinitrogen

First reported - Schrauzer and Guth in 1977 with moist TiO 2 using UV
light
Transfer of e- from CB to N2 directly or indirectly
Potential requirement - N2 reduction and photo-splitting of water - similar
Activation barrier in N2 reduction is high
Reduction of one mole of N2
N2 + 6H+ + 6e-

2 NH3

3H2O + 6h+

3/2 O2 + 6H+

(requires 6 electrons)

Photo-splitting of water
2H+ + 2e-

H2

H2O + 2h+

2H+ + 1/2 O2 (requires 2 electrons)

h+ = hole

Schrauzer G N and Guth T D, J. Am. Chem. Soc., 99 (1977) 7189

24

Problems associated with photo catalytic fixation of N2

Oxidation of NH3 formed to nitrites and nitrates

Recombination of excited electrons

Simultaneous H2 evolution leading to its lesser availability

Less ve conduction band potential of available catalysts

Oxidation reactions by the holes

Lesser adsorption of N2 on catalyst surface

25

Fixation of N2 by iron based catalysts

Fixation of N2 by iron TiO2 based catalysts reported in 1977

CB (Fe2Ti2O7)
CB (TiO2)
N2/NH3

Compound responsible - not established

Fe2Ti2O7 responsible

eV

Has a bandgap of 2 eV
Fe2Ti2O7 Conduction band at 0.4 eV
compared to TiO2 (0.2 eV) high reduction
potential

VB (Fe2Ti2O7)
Band positions of Fe2Ti2O7
1.6

Valence band at +1.6 eV

Rusina O et al, Chem. Eur. J., 9 (2) (2003) 561

26

Mechanism

Fe2Ti2O7 exhibits more activity - presence of ethanol

Exhibits photocurrent doubling in presence of ethanol

Following mechanism explains above two observations

SC (h+,

SC + h

SC (h+,

e-) + H2O

SC (h+) + Had + OH-

SC (h+) + CH3CH2OH
SC + CH3HCOH
SC (e-) + H2O
N2 +

Had

e-)

SC + CH3HCOH + H+
SC (e-) + CH3CHO + H+

Photocurrent
doubling

SC + Had + OHN2H2 or NH3

h+ = hole
SC = Semiconductor

27

Effect of noble metal dispersion

Recombination of electrons and holes - reduces efficiency
Solution - dispersing noble metals on TiO2 surface
Noble metals - high electron affinity - traps excited electrons immediately
e- 2H+ + 2eN2 + 6Had

Trapping of electrons by noble metals

2Had

Metal

Electron
affinity
(eV)

Ru

1.050

Rh

1.136

Pd

0.557

Pt

2.127

Fe

0.163

Ti

0.079

2NH3

Ranjit K T et al, J. Photochem. Photobiol. A: Chem., 96 (1996) 181

28

 Another advantage - reduces H2

evolution
Reduced H+ should be as Had not
evolved as H2
High H2 evolution Low N2 reduction
Noble metals - promote adsorption of
hydrogen on surface

Yield of ammonia (mol h-1)

Effect of noble metal dispersion

Reduction order: Ru > Rh > Pd > Pt

H2 evolution overpotential and M-H bond strength follows same order
Higher loading of metal - lesser activity than TiO 2 - hindrance to light
absorption

29

Fixation of N2 on TiOx- poly-3-methyl thiophene(P3MeT) composite

Drawback - Oxidation of ammonia to nitrites and nitrates
Convert to its salts immediately
A TiOx-conducting polymer doped with ClO4- used
NH3 formed reacts with ClO4- to form NH4ClO4 crystals

N2 reduction and conversion to NH4ClO4

SEM image of NH4ClO4 crystals on polymer

surface

Hoshino K, Chem. Eur. J., 7 (13) (2001) 2727

30

More negative band position

Less negative conduction band (CB) potential Lower rate of reduction

At TiOx-polymer interface - alteration of bandposition - CB at 1.1 eV

CB TiO2 (-0.2 eV)

Increases reduction rate at interface

eV
Polyfuran and polycarbazole - active
Reactivity order:
Carbazole > Furan > Thiophene
Band position change at TiO2-polymer
interface
Tomohisa O et al, J. Photopolym. Sci. Technol., 17 (1) (2004) 143

31

Role of hole scavengers in photo catalytic reduction

Holes in valence band:
Increases recombination
Involve in oxidation of NH3
Necessary to quench the holes formed
Sucrose, acetic acid, salicylic acid, formic acid, methanol and ethanol
- investigated with TiO2
No improvement for sucrose, acetic acid and salicylic acid
Improvement order: formic acid > methanol > ethanol

Tan T et al, J. Photochem. Photobiol. A: Chem., 159 (2003) 273

32

Reduction potential of the radical species

Formic acid, methanol and ethanol form

Potential (eV) vs NHE

reducing radicals
HCOO- + h+

COO- + H+

RCH2OH + h+

RCHOH + H+

RCHOH + SC

RCHO + SC (e-) + H+

Supply electrons to conduction band

Capable of reducing reactant by themselves

N2/NH3

Redox potentials of reaction

species

33

Solvent effects on photo catalytic reduction

Effect of various alcohols as solvents on photo catalytic reduction
Activity order
Methanol > Ethanol > 1-propanol > 2-propanol > 1-butanol > (isobutanol) 2-methyl-propan-1-ol

Properties of solvents which play a role:

Viscosity
Refractive index
Polarity
Stability of radicals

Brezolva V et al, J. Photochem. Photobiol. A: Chem., 107 (1997) 233

34

Properties of the various solvents

High viscosity:
Low diffusion coefficient

High refractive index:

Less penetration of light

High polarity:

Property

Viscosity Refractive
(g cm-1 s-1)
index

Polarity

Solvent
Methanol

0.544

1.326

0.60

Ethanol

1.074

1.359

0.54

1-Propanol

1.945

1.383

0.52

2-Propanol

2.038

1.375

0.48

1-Butanol

2.544

1.397

0.47

iso-Butanol

4.312

1.394

0.40

More stabilization of the charge carriers

Stability:
2-methyl-propan-1-ol(iso-butanol) > 1-butanol > 2-propanol > 1-propanol >
Ethanol > Methanol
Stability of radicals - reverse order of activity

35

Fixation of N2 on a CdS/Pt [RuII(H-EDTA)(N2)]- system

High N2 bond strength - cleavage difficult

Dinitrogen complexation - weakens N-N triple bond - reductively

cleaved by various means

Conventionally reduced using LiAlH4, NaBH4, Al metal

Photoexcited electrons used for the reduction

Nageswara Rao N, J. Mol. Catal., 93 (1994) 23

36

Mechanism

N2 fixation on a CdS/Pt/RuO2 [Ru(H-EDTA)(N2)]- system

EDTA - sacrificial agent enhances rate

Taqui Khan M M and Nageswara Rao N, J. Mol. Catal., 52 (1989) L5

37

Influence of Ti3+ sites on fixation of N2

Adsorption of N2 - essential for e- transfer leading to reduction

Ti3+ defect sites:

Increase N2 adsorption
Responsible for n-type semiconductivity
Directly gives electrons to N2
6 Ti4+-OH
6 Ti3+-OH
6 Ti3+ + N2 + 6 H2O

6 Ti3+-OH
6 Ti3+ + 3 H2O + 3/2 O2
6 Ti4+-OH + 2 NH3

Catalyst with more Ti3+ sites - more active for N2 reduction

Doping TiO2 - favorable preparation methods
Ranjit K T and Viswanathan B, Ind. J. Chem., 35A (1996) 443

38

Yields of ammonia

Not sufficient

Reasons
CB of photo catalyst

Not matching LUMO of N2

N2 adsorption

Not strong to perturb orbitals

39

 The activation of dinitrogen appears to be still intriguing. Even

though, various methods of activation of dinitrogen have been
attempted, the perturbations of the frontier wave functions of
dinitrogen with respect to energy and symmetry have been considered
to be the key.
However, in photocatalytic routes the frontier wave functions of the
reacting species (photo catalysts) are perturbed so as to be able to
interact with ground state wave functions of dinitrogen. It essentially
means that the emphasis is shifted from the reacting species (i.e.
dinitrogen) to the species with which the reacting species interacts.
However, even this shift in the emphasis does not seem to have
provided the answer.

40

41

Ammonia reactants
Steam reforming
CH4(g) + H2O(g) CO(g) + 3 H2(g)
15-40% NiO/low SiO2/Al2O3 catalyst (760-816C)
products often called synthesis gas or syngas
Water gas shift
CO(g) + H2O(g) CO2(g) + H2(g)
Cr2O3 and Fe2O3 as catalyst
carbon dioxide removed by passing through sodium hydroxide.
CO2(g) + 2 OH-(aq) CO32-(aq) + H2O(l)

42

Biological N-Fixation
Most nitrogen is
fixed by microorganisms in the soil
which include
bacteria and
cyanobacteria.

Some plants like

legumes and alder
trees have special
adaptations on
their roots to fix
nitrogen which are
called nodules.
This is an example
of a symbiotic
relationship
between the plant
and N-fixing
bacteria.

NH4Cl + Ba(OH)2 = NH3 + H2O + BaCl

Destructive distillation:
The decomposition of wood by heating out of contact with air,
producing primarily charcoal
Magnesium nitride:
Fomed by interaction of magnesium with nitrogen in atmosphere

Reaction with quick lime:

2NH4Cl + CaO --> 2NH3 + CaCl2 + H2O

44

Structure of RuEDTAN2 complex

N2

45

According to Stokes Einstein equation, Diffusion

coefficient, D = kT/6 r
Where r - radius of species

- viscosity of solvent

46

N2

N2H5+

E = - 0.23 V

N 2H 5 +

NH4+

E = + 1.275 V

N2

NH4+

E = + 0.275 V

47

Structures of polymers

48

49

50

51

Li

Be

Na Mg
K

Ca (Sc) Ti (V) Cr Mn Fe

Rb

Sr

Cs

Ba La (Hf) Ta W Re (Os) Ir
C

Co Ni Cu Zn

Zr Nb Mo (Tc) (Ru) Rh Pd Ag Cd

Pt Au Hg

Al

C
Si

Ga Ge
In Sn
Tl Pb

52

Structural basis of biological nitrogen fixation

Philosophical Transactions of the Royal Society A:
Mathematical, Physical and Engineering Sciences
Volume 363, Number 1829 / April 15, 2005, 971 - 984
Biological nitrogen fixation is mediated by the nitrogenase enzyme
system that catalyses the ATP dependent reduction of atmospheric
dinitrogen to ammonia. Nitrogenase consists of two component
metalloproteins, the MoFe-protein with the FeMo-cofactor that
provides the active site for substrate reduction, and the Fe-protein
that couples ATP hydrolysis to electron transfer. An overview of the
nitrogenase system is presented that emphasizes the structural
organization of the proteins and associated metalloclusters that have
the remarkable ability to catalyse nitrogen fixation under ambient
conditions. Although the mechanism of ammonia formation by
nitrogenase remains enigmatic, mechanistic inferences motivated
by recent developments in the areas of nitrogenase biochemistry,
spectroscopy, model chemistry and computational studies are
discussed within this structural framework.

53

Composition in activated form(%)

Fe2O3
1.1 - 1.7
FeO
14.3 - 14.6
Fe
79.7 - 81.6
CaO
0.1 0.2
SiO2
0.1 0.7
MgO
0.3 - 0.6
Al2O3
1.5 2.1
K2O
0.2 0.5

54

Free-living (asymbiotic)
Cyanobacteria
Azotobacter

Associative
RhizosphereAzospirillum
Lichenscyanobacteria
Leaf nodules

Symbiotic
Legume-rhizobia
Actinorhizal-Frankia
55

56

Structural Basis of Biological Nitrogen Fixation

James B. Howard, Douglas C. Rees
Chem. Rev. 1996, 96, 29652982

57

Why the reduction process is difficult

1 N2(g) + *

N2*

Physisorption

2 N 2* + *

2N*

This is the slow step

3 N* + H*

NH* + *

4 NH* + H*

NH2* + *

NH2* +
H*

NH3* + *

6 NH3*

NH3(g) + *

2* 2NH3 2H* H=-36 kJ/mole

7N2H+2(g)
3H2+

Exothermic

As Temperature increases, should drive the reaction to the left.

But, dissociation is only significant at high temperatures
- Very inefficient reaction (low reaction probability)

58

59

60