Carbon dioxide reduction on Ir(111): stable hydrocarbon surface - - PowerPoint PPT Presentation

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Carbon dioxide reduction on Ir(111): stable hydrocarbon surface - - PowerPoint PPT Presentation

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Contents Introduction Methods Results Conclusions Carbon dioxide reduction on Ir(111): stable hydrocarbon surface species at near-ambient pressure Manuel Corva Physics department, University of Trieste Iom-CNR February 1-11, 2016 |

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Contents Introduction Methods Results Conclusions

Carbon dioxide reduction on Ir(111): stable hydrocarbon surface species at near-ambient pressure

Manuel Corva

Physics department, University of Trieste Iom-CNR

February 1-11, 2016 | Ajdovscina, Slovenia

Manuel Corva

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Contents Introduction Methods Results Conclusions

1

Introduction

2

Methods Near-ambient pressure XPS Non-linear vibronic spectroscopy

3

Results Stable intermediates under reaction conditions Graphene seeding - aromatic compounds

4

Conclusions

Manuel Corva

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Contents Introduction Methods Results Conclusions

CO2 molecule

CO2:

Green house effect Low price Stable: 8.3 eV

MeOH:

Industrial catalyst: Cu/ZnO/Al2O3 50-100 bar 500-550 K Manuel Corva

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Contents Introduction Methods Results Conclusions

Catalytic CO2 reduction in biology

Photosynthesis: Carbon fixation reaction on PS-II, Ca, Mn-containing cluster.

Ferreira, K.N. et al. Science. 303 (2004) 1831

Acetogenic bacteria: Carbon fixation towards acetyl groups, Ni-containing cluster.

Ragsdale, S. W. Chem. Rev. 106 (2006) 3317–3337

Manuel Corva

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Contents Introduction Methods Results Conclusions

Ni(110) surface, CO+CO2+H2 mixtures

Monachino, E. et al., J. Phys. Chem. Lett. 5 (2014) 1929–1934

Highest interaction energy with CO2 (0.6 eV); Surface conditions depend

  • n reaction condition at

NAP regimes!

Manuel Corva

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Contents Introduction Methods Results Conclusions

Ir(111) surface

Why iridium? Ethylene decomposition and graphene growth; CO2 reduction in homogeneous catalysis. Target: CO2 interactions with Ir; Adsorbed species under reaction conditions.

Manuel Corva

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Contents Introduction Methods Results Conclusions Near-ambient pressure XPS Non-linear vibronic spectroscopy

High pressure spectroscopies

Manuel Corva

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Contents Introduction Methods Results Conclusions Near-ambient pressure XPS Non-linear vibronic spectroscopy

NAP-XPS spectroscopy: setup

CAD model

ISISS end station at Bessy2 (Berlin)

Manuel Corva

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Contents Introduction Methods Results Conclusions Near-ambient pressure XPS Non-linear vibronic spectroscopy

IR-Vis SFG spectroscopy

Visp-Lab, Physics Department, University of Trieste Manuel Corva

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Contents Introduction Methods Results Conclusions Near-ambient pressure XPS Non-linear vibronic spectroscopy

IR-Vis SFG spectroscopy: principle

Non linear optics

Lineshape: electronic and vibrational contributions.

Symmetry imposes response only from interfaces!

Manuel Corva

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Contents Introduction Methods Results Conclusions Stable intermediates under reaction conditions Graphene seeding - aromatic compounds

UHV thermal decomposition of ethylene

C-H stretch region

Ethylidyne (CCH3): 2880, 2975 cm−1 Ethynyl (CCH): 3002, 3023 cm−1

Manuel Corva

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Contents Introduction Methods Results Conclusions Stable intermediates under reaction conditions Graphene seeding - aromatic compounds

CO2+CO+H2 mixtures at 0.1 mbar

C-H stretch region

Partial pressure and T dependence Ethylidyne (2904, 2976 cm−1) and ethynyl (3000, 3035 cm−1) Aromatic hydrocarbons (3078 cm−1)

Manuel Corva

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Contents Introduction Methods Results Conclusions Stable intermediates under reaction conditions Graphene seeding - aromatic compounds

Graphenic domains

Carbon core levels region Manuel Corva

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Contents Introduction Methods Results Conclusions

Conclusions

Stable adsorbed species on the surface; Analogy between CO2 reduction and ethylene decomposition; Aromatic fingerprints; Step by step dehydrogenation towards graphene. Manuel Corva

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Contents Introduction Methods Results Conclusions

Acknowledgements

My supervisor: Erik Vesselli

People:

Feng, Zhijing; Dri, Carlo; Comelli, Giovanni;

Financial support:

FIRB2010 COST University of Trieste, Physics Department

Institutions:

CNR-IOM University of Trieste, Physics Department

Manuel Corva

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Contents Introduction Methods Results Conclusions

Thank you for your attention!

Manuel Corva

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Contents Introduction Methods Results Conclusions

CO adsorption and CO2 decomposition

Manuel Corva

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Contents Introduction Methods Results Conclusions

Line shape

PSFG

i

∝ χ(2)

i,j,kE(ωIR)j,kE(ωVis)j,k

it is possible to define a χeff : ISFG(ωIR) ∝

  • A(NR) +

k A(R)

k

ei∆φk ωk −iΓk −ωIR

  • 2

IVisIIR(ωIR)

A(R)

k

amplitude, ∆φk relative phase, ωk frequency, and Γk linewidth

  • f the k-resonance.

Manuel Corva