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NATO

Science for Peace and Security (SPS) Programme

Workshop on CBRN Defence – 22-24 October 2013 – Brussels

Emerging Security Challenges Division

NATO

Brussels. Belgium, 22 october 2013

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UoB (University of Bucharest,

Romania)

EUR (Chemical Center for Defense

NBC and Ecology, CCDNBCE of

Romanian Defense Ministry)

UO (University of Ottawa, Canada)

TUV (Technical University of Valencia, Spain)

NIS (Centre of Excellence Univeristy of Turin,

Italy)

Project Description - SfP 981476

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General overview

• State of the art in destruction of toxic compounds:

- incineration Baseline Technology

- mineralization 1. supercritical water oxidation (SCWO)

2. low temperature, low pressure oxidation processes

A -Chemical Oxidation - considerable waste stream of sulfate and sulfuric acid.

B -Electrochemical Oxidation – high electricity consumption and polymerization of

intermediates to insoluble materials

C -Biological Oxidation – not enough active to be extended in a practical system.

D -Processes Mediated by UV Light - the best application of this technology

appeared to be for the final treatment of dilute solutions after bulk destruction and

oxidation have been accomplished by other means

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General overview

3. high temperature, low pressure pyrolysis processes

A -Molten Metal Processes - the metal furnace does not eliminate the need for a combustion process; the product gases would be oxidized in a separate unit.

B -Plasma arc torches - This feature is suited to the decontamination of metal parts.

C –Gasification - attack on refractory linings by acidic reaction products, such as HF,

might be a problem.

D -“Synthetica” Detoxifier Process

4. high temperature, low pressure oxidation processes

A -catalyzed fluidized bed oxidation - bed, an afterburner would be needed

B -molten sodium carbonate - gaseous effluents would need to be filtered

C -catalytic oxidation - very dilute gas streams for final cleanup

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General overview

- detoxification

1. low temperature liquid phase detoxification (caustic hydrolysis)

2. wet air oxidation (WAO)

- other technologies

1. penetrating ionizing radiation

2. hydrogenation

3. the Adams process

4. underground nuclear detonations

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Synthesis of new photocatalysts for remediation and recovery of

land and materials exposed to chemical weapons exhibiting a high

activity and efficiency for a large plethora of compounds

Overall objective

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1. Design of a series of photocatalysts in which a photoactive guest is

incorporated/protected within the pores of zeolites having or not co-

operating acid or basic sites.

Specific objectives

MN

N

N

N

N

N

N

N

O+

Metalo-phthalocyanines

2,4,6-Triphenylpyrylium

Electron-donor Electron-acceptor

The photoactive guests include organic dyes, metallic complexes and clusters of inorganic semiconductors.

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Specific objectives

MN

N N

N

N

N

N

N

CN

CN

M@NaY

250oC4

O+ O O O O

O+

OH

O

H2O

pH=7absorption 200oC

Synthesis pathways

Metalophthalocyanines reclusion

2,4,6-Triphenylpyrylium reclusion

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2. Design of new microporous silicotitanate with narrowed band gap with

the scope to increase the adsorption capacity and photocatalytic

efficiency.).

Specific objectives

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3. Photochemical studies and photocatalytic degradation tests with the

series of new solid photocatalysts. Determination of the nature and

lifetimes of excited states and intermediates involved in the photocatalysis

by time-resolved submillisecond techniques.

Specific objectives

4. Identification of the detailed mechanism of model compounds

degradation

5. Assessment of the surface modification due to adsorption of stable

products (sulfate, phosphate species, oxidation products)

6. Evaluation of catalytic performance in relation to surface speciation and

protocols in order to avoid catalyst deactivation due to surface deposition

of stable products

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• New technologies to produce high functionalized materials.

• Protocols for preparation of mixtures with photocatalytic activity

• Rapid cleaning and decontamination of surfaces from chemical

weapons with total recovery of the exposed surfaces.

Outcomes

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Results

Target molecules

Yperite

(sulfur mustard)

Soman

(GD)

VX

Derived from pesticides

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Results

Experimental protocols

UV Vis

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Results

Experimental protocols

UV Vis

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Results

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Results

CB

VB 400 600 800 1000

0

10

20

30

F(R

)

Wavelength, nm

Interactions between guest molecule and support (not only physical reclusion.

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Results

D2O

46 µs

100 200 300 400 5000-0,01

0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0

-0,01

-0,02

-0,03

-0,04

-0,05

-0,06

1200 1250 1300 1350Lungime de unda, nm

Timp, μs

Inte

nsit

ate

aem

isie

i. V

DFP

470±30 µs

7 µs

100 200 300 400 5000

0

0,05

0,1

0,15

0,2

0,25

0,01

0,1

Timp, μs

Inte

nsit

ate

aem

isie

i, V

0 100 200 300 400

Generation of Singlet Oxygen

(very reactive species)!!!!

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Results

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PO

F

O

PO

OH

O

POH

OH

OHO

OP

SO

N

OP

S

OH

ON

OP

OH

OS N

HO

ClS

Cl

Results

Vis

PO

F

O

OP

SO

N

ClS

Cl

UV

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Results

Best dopants:

- Mn for naturally aerated

- V for controlled air flow

* Impreganted or sol-gel

Combined effect:

-Vis response from N

- adsorptive capabilities from AC

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Results

Yperite

Up to 98% decontamination in 2 hours

Soman

Mineralization in less than 90 min

TiO2

Carbon nano

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- new materials and procedures for decontamination of surfaces

(indoor and outdoor)

- first evidence of the generation of singlet oxygen for confined

photosensitizers

- application in real conditions

- 2 PhD thesys

- 9 scientific articles

Project Outcome

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Project Outcome

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• The results of the project led to technologies for preparation of

efficient photocatalysts for the destruction of several chemical

weapons under mild and easy applicable conditions

• The project proposes photocatalytic solutions for the destructions

of the indicated chemical weapons as a consequence of undesired

terrorist attack.

• These solutions represent a contribution of the project to CRBN

defense

Impact

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• These achievements do not represent “the end” and further

improvements are necessary!

• To ensure these improvements the SPS Programme in CBRN

Defense should also include the photocatalytic destruction of

chemical weapons and derivatives as an important target.

Way Forward – SPS CBRN