Carbon dioxide reduction mechanism on Ru-based electrocatalysts [Ru(bpy)2(CO)2]2+: insights from first-principles theory

Damas, Giane B.; Ivashchenko, Dmytro A.; Rivalta, Ivan; Araújo, C. Moysés

doi:10.1039/d1se01315g

Cited by 5 publications

(5 citation statements)

References 63 publications

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“…Due to the acidity of Zr cations, this interaction is described as a σ‐bond with a coordinate covalent nature [42] . This bond has a low binding energy of −50.3 kJ/mol, and d(C−Zr)=2.62 Å, as expected for 5 th ‐ period complexes with CO ligand coordination, [48] with slight transfer of electric charge verified in the populational analysis. Maleki et al .…”

Section: Resultssupporting

confidence: 67%

“…Therefore, this adsorption mode is shifted upwards in comparison with CO(g), a trend that was associated with the CO polarization after adsorption by Kondo et al [47] Due to the acidity of Zr cations, this interaction is described as a σbond with a coordinate covalent nature. [42] This bond has a low binding energy of À 50.3 kJ/mol, and d(CÀ Zr) = 2.62 Å, as expected for 5 th -period complexes with CO ligand coordination, [48] with slight transfer of electric charge verified in the populational analysis. Maleki et al determined similar values for the adsorption energy E ads (CÀ Zr) using ZrO 2 nanoparticles of larger size within the GGA + U/1-1-1 level of theory.…”

Section: Zro 2 (S) Interacting With H 2 and Cosupporting

confidence: 60%

“…The Gibbs free energy in gas phase G for each species is defined similarly to the description given in ref. [48,67]…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

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Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study

Kalered,

Damas,

Mäkie

et al. 2023

ChemCatChem

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The methanol economy is an attractive approach to tackle the current concerns over the depletion of natural resources and the global warming intrinsically associated with the use of fossil fuels. This can be achieved by hydrogenation of carbon dioxide to produce methanol, a liquid fuel with potential use in civil transportation. In this study, we aim to pinpoint the intermediates that are involved in the catalytic CO2 conversion into methanol on pure zirconia (ZrO2), Cu and Cu/ZrO2 systems. To accomplish this, we make use of infrared (IR) spectroscopy measurements and quantum chemical simulations within the hybrid density functional theory (DFT) framework. At 250 °C and p~30 bar, the main species formed on the partially hydroxylated ZrO2 is bidentate formate, whereas the co‐production of bicarbonate is relevant upon cooling to T=25 °C. On pure Cu, the IR fingerprints of methanol and carbon dioxide indicate their presence in the gas phase and surface environment, albeit formate/formic acid and methoxy species are also detected at these experimental conditions. The production of methanol on Cu/ZrO2 is mostly dependent on the Cu catalyst, but the higher amount of the methoxy intermediate can be correlated with the consumption of formate adsorbed on ZrO2 or at the Cu/ZrO2 interface. On the Cu/ZrO2 mixture, the reaction mechanism is likely to involve formate as the main intermediate, instead of CO which would result from the reverse water‐gas shift reaction. Ultimately, the higher activity shown by the Cu/ZrO2 mixture might be associated with the extra‐production of methoxy/methanol catalyzed by ZrO2 in the presence of Cu.

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Section: Resultssupporting

confidence: 67%

Section: Zro 2 (S) Interacting With H 2 and Cosupporting

confidence: 60%

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Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study

Kalered,

Damas,

Mäkie

et al. 2023

ChemCatChem

Self Cite

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“…For each species, the Gibbs free energy in gas phase G is defined similarly to the description given in ref. 51,52 At the start, the precursor dissociation is considered a reversible process described by the equilibrium constant Keq, a thermodynamic property that is computed through the relation…”

Section: 2-thermodynamic Calculationsmentioning

confidence: 99%

Thermal Decomposition of Trimethylindium and Indium Trisguanidinate Precursors for InN Growth: An Ab-Initio and Kinetic Modelling Study

Damas¹,

Rönnby

Pedersen

et al. 2023

Preprint

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Indium nitride (InN) is an interesting material for future electronic and photonic-related applications, as it combines high electron mobility and low-energy band gap for photoabsorption or emission-driven processes. In this context, atomic layer deposition (ALD) techniques have been previously employed for InN growth at low temperatures (typically < 350 C), reportedly yielding crystals with high quality and purity. In general, this technique is assumed to not involve any gas phase reactions as a result from the time-resolved insertion of volatile molecular sources into the gas chamber. Nonetheless, such temperatures could still favour the precursor decomposition in gas phase during the In half-cycle, therefore altering the molecular species that undergoes physisorption and, ultimately, driving the reaction mechanism to pursue other pathways. Thence, we herein evaluate the thermal decomposition of relevant In precursors in gas phase, namely trimethylindium (TMI) and tris(N,N-diisopropyl-2-dimethylamido-guanidinato) (III) (ITG), by means of thermodynamic and kinetic modelling. According to the results, at T= 593 K, TMI should exhibit partial decomposition of ~8% after 400 s to first generate methylindium (MI) and ethane (C2H6), a percentage that increases to ~34% after 1 hour of exposure inside the gas chamber. Therefore, this precursor should be present in an intact form to undergo physisorption during the In half-cycle of the deposition experiment (< 10 s). On the other hand, the ITG decomposition starts already at the temperatures used in the bubbler and it will slowly decompose as it is evaporated during the deposition process. At T= 300 C, the decomposition is a fast process that reaches 90% completeness after 1 s, and where equilibrium, at which almost no ITG remains, is achieved before 10 s. In this case, the decomposition pathway is likely to occur via elimination of carbodiimide ligand. Ultimately, these results should contribute for a better understanding of the reaction mechanism involved in the InN growth from these precursors.

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“…73 Molecular Ru(N^N) 3 and Ir(C^N) 2 (X^N) complexes have been widely employed in various photosynthesis reactions, such as the HER, 74,75 CO 2 RR, [76][77][78] water oxidation, 79,80 and particularly in organic transformations including electron transfer reactions, H atom transfer reactions and energy transfer reactions. [81][82][83] Ru(N^N) 3 and Ir(C^N) 2 (X^N) functionalized architectures exhibit numerous applications from luminescence, 7,84,85 sensing, 86 solar fuels 87,88 to bioimaging [89][90][91] and furthermore, photocatalytic activity is always the most intriguing performance. [92][93][94][95][96][97][98] They have great advantages in the photocatalysis system due to the following: (1) their light adsorption ranges are tunable from visible light to the near-providing a platform for the efficient utilization of solar energy.…”

mentioning

confidence: 99%

Polypyridyl Ru(ii) or cyclometalated Ir(iii) functionalized architectures for photocatalysis

Liu

Huang

et al. 2023

Chem. Soc. Rev.

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Carbon dioxide reduction mechanism on Ru-based electrocatalysts [Ru(bpy)₂(CO)₂]²⁺: insights from first-principles theory

Abstract: Solar fuel production through the so-called artificial photosynthesis has attracted a great deal of attention to the development of a new world energy matrix that is renewable and environmentally friendly.

Cited by 5 publications

References 63 publications

Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study

Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study

Thermal Decomposition of Trimethylindium and Indium Trisguanidinate Precursors for InN Growth: An Ab-Initio and Kinetic Modelling Study

Polypyridyl Ru(ii) or cyclometalated Ir(iii) functionalized architectures for photocatalysis

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Carbon dioxide reduction mechanism on Ru-based electrocatalysts [Ru(bpy)2(CO)2]2+: insights from first-principles theory

Abstract: Solar fuel production through the so-called artificial photosynthesis has attracted a great deal of attention to the development of a new world energy matrix that is renewable and environmentally friendly.

Cited by 5 publications

References 63 publications

Infrared Fingerprints of the CO2 Conversion into Methanol at Cu(s)/ZrO2(s): An Experimental and Theoretical Study

Infrared Fingerprints of the CO2 Conversion into Methanol at Cu(s)/ZrO2(s): An Experimental and Theoretical Study

Thermal Decomposition of Trimethylindium and Indium Trisguanidinate Precursors for InN Growth: An Ab-Initio and Kinetic Modelling Study

Polypyridyl Ru(ii) or cyclometalated Ir(iii) functionalized architectures for photocatalysis

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Product

Resources

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Carbon dioxide reduction mechanism on Ru-based electrocatalysts [Ru(bpy)₂(CO)₂]²⁺: insights from first-principles theory

Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study

Infrared Fingerprints of the CO₂ Conversion into Methanol at Cu(s)/ZrO₂(s): An Experimental and Theoretical Study