Imaging and characterization of activated<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mtext>CO</mml:mtext></mml:mrow><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>species on Ni(110)

Dri, Carlo; Peronio, Angelo; Vesselli, Erik; Africh, Cristina; Rizzi, Michele; Baldereschi, A.; Peressi, Maria; Comelli, Giovanni

doi:10.1103/physrevb.82.165403

Cited by 33 publications

(10 citation statements)

References 19 publications

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“…Activation of carbon dioxide by charge doping of the molecule through transfer from a catalytic active surface has been extensively studied during the last several years. These works include experimental and theoretical investigations of vacuum adsorption of CO

at low temperatures on metal surfaces [ 14 , 15 , 16 , 17 ] as well as experiments at higher pressures [ 18 , 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Carbon Dioxide on Mono-Layer Thick Oxidized Samarium Films on Ni(100)

Raaen

2021

Nanomaterials

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Studies of adsorption of CO2 on nanoscopic surfaces are relevant for technological applications in heterogeneous catalysis as well as for sorption of this important greenhouse gas. Presently, adsorption of carbon dioxide on pure and oxidized thin samarium layers near mono-layer thickness on Ni(100) has been investigated by photoelectron spectroscopy and temperature programmed desorption. It is observed that very little CO2 adsorb on the metallic sample for exposures in the vacuum regime at room temperature. For the oxidized sample, a large enhancement in CO2 adsorption is observed in the desorption measurements. Indications of carbonate formation on the surface were found by C 1s and O 1s XPS. After annealing of the oxidized samples to 900 K very little CO2 was found to adsorb. Differences in desorption spectra before and after annealing of the oxidized samples are correlated with changes in XPS intensities, and with changes in sample work function which determines the energy difference between molecular orbitals and substrate Fermi level, and thus the probability of charge transfer between adsorbed molecule and substrate.

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at low temperatures on metal surfaces [ 14 , 15 , 16 , 17 ] as well as experiments at higher pressures [ 18 , 19 , 20 , 21 , 22 ].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Carbon Dioxide on Mono-Layer Thick Oxidized Samarium Films on Ni(100)

Raaen

2021

Nanomaterials

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“…The presence of the N-species on the carbon substrate both stabilizes the active Fe(II) centers hindering further reduction of Fe, thus inhibiting the hydrogen evolution, and allows coordination of the reactive CO 2 -related species related with the liquid phase [142]. Interestingly, it is found that the latter (H 2 CO 3 , HCO 3 − , CO 3 − ) consistently differ with respect to their counterpart in the case of the solid/gas reaction [68][69][70][71][72][144][145][146]. Metal-nitrogen coordinated electrocatalytic systems offer the capability of electron donation/ withdrawal to/from the carbonaceous ligand, thus with improved and tunable activity [147][148][149][150].…”

Section: 1mentioning

confidence: 98%

“…A few surface science examples are reported in the literature [8,14], in which a biomimetic approach is exploited to engineer the first, most difficult step consisting in the activation of the molecule. CO 2 is indeed a closed shell, very stable molecule and its activation is obtained by injecting negative charge in it, thus yielding a bent, 'V' shaped precursor that is chemically reactive [68][69][70][71][72]. In Nature this step is performed by the enzyme Ribulose−1,5-bisphosphate carboxylase oxygenase (RuBisCO) where the active conversion center incorporates a Mg 2+ ion.…”

Section: Tetrapyrroles and Mofs At Surfaces Under Uhv Conditions: A Fmentioning

confidence: 99%

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

Vesselli

2020

J. Phys. Mater.

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Many complex mechanisms underlying the fascinating functionalities provided by tetrapyrrolic macrocycles in biochemistry have been already unraveled. Light harvesting, molecular transport, and catalytic conversion are some of the processes performed by tetrapyrrole-based centers embedded in protein pockets. The main function is determined by the single atom species that is caged in the macrocycle, while a finer tuning (band gap, chemical selectivity etc) is granted by the geometric and electronic structure of the tetrapyrrole, including its residues, and by the proximal and distal structures of the protein surroundings that exploit the molecular trans-effect and direct weak interactions, respectively. Hence, a scientific and technological challenge consists in the artificial replication of both structure and functionality of natural reaction centers in 2D ordered arrays at surfaces. Nano-architected 2D metalorganic frameworks can be indeed self-assembled under controlled conditions at supporting surfaces and, in the specific, porphyrin-and phthalocyaninebased systems have been widely investigated in ultra-high vacuum conditions by means of surface science approaches. Deep insight into the geometry, electronic structure, magnetic properties, ligand adsorption mechanisms, and light absorption has been obtained, with the strong experimental constraint of vacuum. Especially in the case of the interaction of tetrapyrroles with ligands, this limit represents a relevant gap with respect to both comparison with natural counterparts from the liquid environment and potential applicative views at both solid-liquid and solid-gas interfaces. Thus, a step forward in the direction of near-ambient pressure is strongly necessary, while maintaining the atomiclevel detail characterization accuracy. Nowadays this becomes feasible by exploiting state-of-the-art experimental techniques, in combination with computational simulations. This review focusses on the latest advances in this direction.

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“…[15] Several computational studies have also been carried out to investigate the interactions of CO2 with Ni, mostly employing the spinpolarized density functional theory-generalized gradient approximation (DFT-GGA) to understand the energetics on their various topologies. [16][17][18][19][20][21][22][23][24] CO2 is reported to bind more strongly on iron than nickel while its decomposed species bind stronger to nickel than iron. Kinetically decomposition is observed to be favored on iron than nickel.…”

Section: Introductionmentioning

confidence: 99%

First-Principles DFT Insights into the Mechanisms of CO2 Reduction to CO on Fe (100)-Ni Bimetals

Kwawu

Aniagyei

Konadu

et al. 2021

Preprint

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Iron and nickel are known active sites in the enzyme carbon monoxide dehydrogenases (CODH) which catalyzes CO2 to CO reversibly. The presence of nickel impurities in the earth abundant iron surface could provide a more efficient catalyst for CO2 degradation into CO, which is a feedstock for hydrocarbon fuel production. In the present study, we have employed spin-polarized dispersion-corrected density functional theory calculations within the generalized gradient approximation to elucidate the active sites on Fe (100)-Ni bimetals. We sort to ascertain the mechanism of CO2 dissociation to carbon monoxide on Ni deposited and alloyed surfaces at 0.25, 0.50 and 1 monolayer (ML) impurity concentrations. CO2 and (CO + O) bind exothermically i.e., -0.87 eV and − 1.51 eV respectively to the bare Fe (100) surface with a decomposition barrier of 0.53 eV. The presence of nickel generally lowers the amount of charge transferred to CO2 moiety. Generally, the binding strengths of CO2 were reduced on the modified surfaces and the extent of its activation was lowered. The barriers for CO2 dissociation increased mainly upon introduction of Ni impurities which is undesired. However, the 0.5 ML deposited (FeNi0.5(A)) surface is promising for CO2 decomposition, providing a lower energy barrier (of 0.32 eV) than the pristine Fe (100) surface. This active 1-dimensional defective FeNi0.5(A) surface provides a stepped surface and Ni-Ni bridge binding site for CO2 on Fe (100). Ni-Ni bridge site on Fe (100) is more effective for both CO2 binding or sequestration and dissociation compared to the stepped surface providing the Fe-Ni bridge binding site.

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Imaging and characterization of activatedCO2species on Ni(110)

Cited by 33 publications

References 19 publications

Adsorption of Carbon Dioxide on Mono-Layer Thick Oxidized Samarium Films on Ni(100)

Adsorption of Carbon Dioxide on Mono-Layer Thick Oxidized Samarium Films on Ni(100)

Tetrapyrroles at near-ambient pressure: porphyrins and phthalocyanines beyond the pressure gap

First-Principles DFT Insights into the Mechanisms of CO2 Reduction to CO on Fe (100)-Ni Bimetals

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