Inmaculada Rodrguez Ramos Nanostructured catalysts for sustainable - - PowerPoint PPT Presentation

Instituto de Cat Instituto de Catá álisis y Petroleoqu lisis y Petroleoquí ímica (ICP) mica (ICP) “ “Institute Institute of

• f Catalysis

Catalysis and and Petroleochemistry Petroleochemistry” ” Inmaculada Rodríguez Ramos “Nanostructured catalysts for sustainable chemical processes”

http://www.icp.csic.es

Main Research Lines Main Research Lines

Main general objective for the three research lines: to develop both advanced catalysts and innovative chemical processes. ENERGY LINE. Catalysts and catalytic processes for the production and transformation of energy resources. ENVIRONMENT PROTECTION LINE. Catalysts and catalytic processes for pollutant abatement and disinfection. LINE OF SELECTIVE SYNTHESIS OF CHEMICALS. Catalysts and processes for the synthesis of commodities and high value added chemicals.

Sublines Sublines in the Energy Field in the Energy Field

FUEL CELLS.

PRODUCTION AND USES OF HYDROGEN. COMPETITIVE AND SUSTAINABLE PRODUCTION OF FUELS.

The general objective of the Energy Line is the development

• f new catalysts and electrocatalysts for the chemical

conversion of renewable energy resources into hydrogen, liquid fuels and chemicals. Such processes include biomass transformation into fuels and chemicals, upgrading of non- edible oils and glycerol, synthesis of liquid hydrocarbons from carbon oxides, and production of electricity in FCs using both H2 and organic carriers.

Fuel Fuel Cells Cells

Proton Exchange Membrane Fuel Cells (PEMFC) Research, development and fabrication of FC Electrocatalysts Optimization of inorganic (Pt-based) electrodes Development of new active phases for substitution of platinum as main active metal (anode and cathode). Metalloenzimes-based electrodes: Development of interfaces for efficient electron transfer between metalloenzymes that activate H2 and O2 and electrodes as an alternative to Pt-based electrodes Solid Oxide Fuel Cells (SOFC) New catalytic formulations for intermediate temperature direct fuel oxidation.

Biofuel Biofuel cells cells

• M. Asuncion Alonso-Lomillo et al., NanoLetters 7 (2007) 1603.

573 648 723 798 873 948 1023 1098 1173

Cu-CeGd CuNi-Ce CuNi-CeGd CuNi-CeTb CO2 signal (a.u.) Temperature (K)

SOFC

CH4-TPR

20 30 40 50 60 70 80 Ni

+ Ce2O3 * fluorite (Ce,M)Ox # Cu-Ni alloy

# # + + + + + + + +

* * * * * * * CuNi-CeTb CuNi-CeGd a.u. 2θ (

• )

CuNi-Ce *

+ #

Cu

XRD

YSZ Cu CeO2 CGO Cu (Ce,M)Ox Cu-M YSZ Cu CeO2 CGO Cu (Ce,M)Ox Cu-M CGO Cu (Ce,M)Ox CGO Cu (Ce,M)Ox Cu-M Cu-M

• A. Hornés et al. Journal of Power Sources 169 (2007) 9–16 and in press (doi:10.1016/j.jpowsour.2008.12.015)

General projects dealing with hydrogen as clean energy vector as well as including full hydrocarbon

• r biofuel processing for production of hydrogen

usable in fuel cells. Electrolysis of water/sacarose solutions. CO2-free alternatives. Visible-light water photodissociation. Diesel reforming. Natural gas catalytic decomposition. WGS or CO-PROX with Pt-free catalysts. Production Production and and uses uses of

• f Hydrogen

Hydrogen

Production Production and and uses uses of

• f Hydrogen

Hydrogen

300 350 400 450 500 550 10 20 30 40 50 60 70 80 90 100 110

Selectividad Temperatura / K

0,5Cu 1Cu 3Cu 5Cu Ce0,95Cu0,05O2 Ce0,9Cu0,1O2 Ce0,8Cu0,2O2

300 350 400 450 500 550 20 40 60 80 100

%Conversión de CO Temperatura / K

0,5Cu 1Cu 3Cu 5Cu Ce0,95Cu0,05O2 Ce0,9Cu0,1O2 Ce0,8Cu0,2O2

Ce0.8Cu0.2O2

CuO

CeO2 support Reduced interface Massive copper

• xide reduction

CO+O2 H2+O2 CO-PROX ACTIVITY

• D. Gamarra et al. Journal of the American Chemical Society 129 (2007) 12064

Production Production and and uses uses of

• f Hydrogen

Hydrogen

Fullerenes

• J. Álvarez-Rodríguez, unpublished results.

Carbon Carbon nanotubes nanotubes based catalysts based catalysts

Carbon 44 (2006) 799–823 Diamond & Related Materials 16 (2007) 542–549 Nano Lett., 7, (2007) 1603

350 400 450 20 40 60 80 Conv (%) T (ºC)

Conversion in ammonia decomposition reaction (●) RuCNTs-0, (■) RuCNTs-N, () RuCNTs-1 and (▼) RuCNTs-2

CNTs and N-doped CNTs Selective confinement of discrete nanoparticles (NPs) in the CNT cavity. Catalytic performance in FT and CO-PROX.

Metal supported systems for abatements of

• rganic pollutants in contaminated waters.
• Aniline and phenol oxidation in water.
• M. Soria et al, Carbon, in press.

In subsequent cycles the Fe/C ratio remains constant and the catalytic activity is almost equivalent during all reaction cycles.

60 120 180 240 300 20 40 60 80 100 60 120 180 240 300 20 40 60 80 100

Phenol conversion (%) Reaction time (min) a Mineralization (%) Reaction time (min) b

Evolution of (a) conversion and (b) mineralization with the reaction time in the CWAO of Phenol over: (□) CNFs; (○) ox/CNFs; (∆) acac/CNFs; (■) Fe(II)-CNFs; (●) Fe(II)-ox/CNFs; (▲) Fe(II)- acac/CNFs.

Sunlight excitation Sunlight excitation

Liquid Liquid: : Phenol Phenol Intimate structure Intimate structure-

• activity link

activity link

3 6 9 12 15 18 21 1 2 3 9.5 9.6 9.7 9.8 9.9 10.0

TiO 2 (nano)

% (W /(W +Ti)) (ICP-AAS analysis)

Rate / 10

• 10 mol s
• 1 m
• 2

TiO 2

x 3.3 x 3.0 P25

W W-N

50 100 150 200 250 300 350 50 60 70 80 90 100 TiO2 TiFe-0.4 TiFe-0.7 TiFe-1.5 TiFe-3.5 TiFe-5.1 TiO2-A

[TOC] (%) Time (min)

1 2 3 4 5 6 5 10 15 20 25 30 35 40 45

conversion (%) Fe content (%)

• A. Kubacka Chem. Comm. 2001; Appl. Catal. B 72 (2007) 11; 74 (2007) 26

Gas: Gas: Toluene Toluene TiO2 modification: cationic/anionic doping TiO2 modification: cationic/anionic doping

• Cationic: Fe, V (low loaded samples)

Cationic: Fe, V (low loaded samples) Mo, W (high loaded samples) Mo, W (high loaded samples)

• Anionic: N;

Anionic: N; “ “self self-

• doped

doped” ” samples samples

• Both: W

Both: W-

• N

N

Self-sterilized Plastic Materials

Capabilities Capabilities strong germicidal ( strong germicidal (biofilm biofilm) ) controlled self controlled self-

• degradation

degradation Optimum 2 Optimum 2-

• 5 wt%

5 wt% Ag; visible Ag; visible-

• light active materials

light active materials

2 4 6 8 10 12 14

Cell Number / 10

• 4 mm

2

EVOH 2AgTi, no UV 05Ti 05TiAg 2Ti 2TiAg 5Ti 5TiAg

EVOH EVOH-Ti2 EVOH-Ti2 EVOH-Ti5 EVOH-Ti5 EVOH-Ti0.5

Kubacka et al. Nano Letters 7 (2007) 2529 Advanced Functional Materials 18 (2008) 1949

• Env. Sic. Technol.43 (2009) 1630; J. Phys. Chem. C (accepted).

http://www.icp.csic.es/

Institute Institute of

• f Catalysis

Catalysis and and Petroleochemistry Petroleochemistry