NATO Science for Peace and Security (SPS) Programme Workshop on CBRN Defence October 2013 Brussels
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1 AT Science for Peace and Security (SPS) Programme Workshop on CBR Defence ctober 2013 Brussels Emerging Security Challenges Division AT Brussels. Belgium, 22 october
2 Project Description - SfP U (University of ttawa, Canada) TUV (Technical University of Valencia, Spain) IS (Centre of Excellence Univeristy of Turin, Italy) UoB (University of Bucharest, Romania) EUR (Chemical Center for Defense BC and Ecology, CCDBCE of Romanian Defense Ministry) 2
3 General overview State of the art in destruction of toxic compounds: - incineration Baseline Technology - mineralization 1. supercritical water oxidation (SCW) 2. low temperature, low pressure oxidation processes A -Chemical xidation - considerable waste stream of sulfate and sulfuric acid. B -Electrochemical xidation high electricity consumption and polymerization of intermediates to insoluble materials C -Biological xidation 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 3
4 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 4
5 General overview - detoxification 1. low temperature liquid phase detoxification (caustic hydrolysis) 2. wet air oxidation (WA) - other technologies 1. penetrating ionizing radiation 2. hydrogenation 3. the Adams process 4. underground nuclear detonations 5
6 verall objective 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 6
7 Specific objectives 1. Design of a series of photocatalysts in which a photoactive guest is incorporated/protected within the pores of zeolites having or not cooperating acid or basic sites. Metalophthalocyanines 2,4,6- Triphenylpyrylium M + Electron-donor Electron-acceptor The photoactive guests include organic dyes, metallic complexes and clusters of inorganic semiconductors. 7
8 Specific objectives Synthesis pathways Metalophthalocyanines reclusion 4 C C M@aY 250 o C M 2,4,6-Triphenylpyrylium reclusion H H 2 ph=7 absorption 200 o C + + 8
9 Specific objectives 2. Design of new microporous silicotitanate with narrowed band gap with the scope to increase the adsorption capacity and photocatalytic efficiency.). 9
10 Specific objectives 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. 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 10
11 utcomes ew 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. 11
12 Results Target molecules Yperite (sulfur mustard) Soman (GD) Derived from pesticides VX 12
13 Results Experimental protocols UV Vis 13
14 Results Experimental protocols UV Vis 14
15 Results 15
16 F(R) Results Interactions between guest molecule and support (not only physical reclusion. 30 CB Wavelength, nm VB 16
17 Intensitatea emisiei, V Intensitatea emisiei. V Results 0,07 0,06 0,05 0,04 0,03 0,02-0,06-0,05-0,04-0,03-0,02-0, Lungime de unda, nm 1350 D 2 46 µs Generation of Singlet xygen (very reactive species)!!!! 0,01 0-0, Timp, μs 0,25 DFP 7 µs 470±30 µs 0,2 0,15 0,1 0, ,1 0, Timp, μs 17
18 Results 18
19 19 P F P H P H H H P S P S H P H S H Cl S Cl Results Vis P F P S Cl S Cl UV
20 Results Best dopants: - Mn for naturally aerated - V for controlled air flow * Impreganted or sol-gel Combined effect: -Vis response from - adsorptive capabilities from AC 20
21 Results Ti2 Carbon nano Yperite Up to 98% decontaminat ion in 2 hours Soman Mineralization in less than 90 min 21
22 Project utcome - 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 22
23 Project utcome 23
24 Impact 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 CRB defense 24
25 Way Forward SPS CBR These achievements do not represent the end and further improvements are necessary! To ensure these improvements the SPS Programme in CBR Defense should also include the photocatalytic destruction of chemical weapons and derivatives as an important target. 25
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