Suppression of surfaces states at cubic perovskite (001) surfaces by CO<sub>2</sub> adsorption

Sopiha, Kostiantyn V.; Malyi, Oleksandr I.; Persson, Clas; Wu, Ping

doi:10.1039/c8cp02535e

Cited by 14 publications

(16 citation statements)

References 77 publications

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“…O 1s XPS peaks in the spectrum of the PbTiO 3 nanocatalyst collected after exposure to CO 2 gas were rarely different from their counterparts in the spectrum collected pre-exposure. The XPS peaks of Ba, Sr, and Ca indicated that CO 2 chemisorption at A-metal sites (Ba and Ca > Sr) was preferred over chemisorption at Ti sites due to their lower adsorption energies Figure S37b shows the ratios of produced carbon to A-site atoms (C/A; A = Ba, Sr, Ca, or Pb).…”

Section: Results and Discussionmentioning

confidence: 99%

“…The mechanism of CO 2 reduction into nanodiamond and graphitic structures on the nanocatalysts shown in Figure was estimated by CO 2 chemisorption and reaction mechanism on perovskite-type materials in the preceding works, as mentioned below. A CO 2 chemisorption site was evaluted from ab initio calculations on (001) surfaces of ABO 3 perovskite . CO 2 was highly stable to be adsorbed on A sites with a CO 3 -like complex rather than on B sites.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The XPS peaks of Ba, Sr, and Ca indicated that CO 2 chemisorption at A-metal sites (Ba and Ca > Sr) was preferred over chemisorption at Ti sites due to their lower adsorption energies. 73 Figure S37b shows the ratios of produced carbon to A-site atoms (C/A; A = Ba, Sr, Ca, or Pb). The amounts of carbon deposited on BaTiO 3 and CaTiO 3 nanocatalysts were 8−50 times larger than those deposited on SrTiO 3 and PbTiO 3 nanocatalysts, which were further evidence of CO 2 thermal reduction on BaTiO 3 and CaTiO 3 nanocatalysts.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…perovskite. 73 CO 2 was highly stable to be adsorbed on A sites with a CO 3 -like complex rather than on B sites. CO 2 chemisorption on A sites of nanocatalysts was also observed from the XPS analyses in this work.…”

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 97%

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Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Watanabe

Ohba

2021

ACS Sustainable Chem. Eng.

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Catalytic thermal reduction of CO 2 has the potential to minimize the energy requirement in carbon capture and utilization. However, this process necessitates high energy with a reactant gas, heating, and pressurization. High-performance catalysts are thus needed to transform CO 2 into value-added carbon products at low energy consumption. We here demonstrate the thermal reduction of CO 2 to carbon products at 700 K and ambient pressure using nanoscale perovskite-type titanium nanocatalysts. The reactivity of CO 2 was exponentially increased by decreasing the particle size until 10 nm. The reaction yields calculated from the weight changes of nanocatalysts under CO 2 flow were very high, i.e., between 1600 and 3300 μmol g −1 h −1 for nanocatalysts smaller than 20 nm, which were similar to those of CO 2 reductions with a reactant gas into lower hydrocarbons and alcohols. A CO 2 reductant was evaluated by transmission electron microscopy, chemical mapping using energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman scattering spectroscopy. Graphitic carbons were coated on 9−12 nm nanocatalysts after CO 2 reduction. Graphitic carbons were mainly observed on the 12 nm nanocatalyst. A nanodiamond-like structure was partly observed on the 9 nm nanocatalyst, as well as a graphitic structure. Nanodiamond was hardly produced in the mild condition at 700 K and ambient pressure, which was normally produced above 2 GPa and 1600 K. A nanodiamond was produced by quasi-high-pressure effect in graphene and amorphous carbons, which were previously produced on nanocatalysts. The low-temperature CO 2 thermal reduction using perovskite-type titanium nanocatalysts at 700 K is thus a promising approach to CO 2 reduction and novel way to produce nanodiamond-like structure.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Acs Sustainable Chemistry and Engineeringmentioning

confidence: 97%

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Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Watanabe

Ohba

2021

ACS Sustainable Chem. Eng.

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“…The results show that CO 2 molecules can suppress the surface states of SiO 2 , which is consistent with previous research. 64,65 Meanwhile, they can also activate new electronic energy states via carbonation reaction.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Molecular Dynamics Study of Carbonation and Hydrolysis Reactions on Cleaved Quartz (001) Surface

et al. 2019

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Geochemical trapping (i.e., mineralization) is considered to be the most efficient way for long-term CO2 storage in order to mitigate “global warming effect” induced by anthropogenic CO2 emission. The common view is that the reaction process takes hundreds of years; however, recent field pilots have demonstrated that it only took 2 years to convert injected CO2 to carbonates in reactive basaltic reservoirs. In this work, ab initio molecular dynamics simulations were employed to investigate chemical reactions among CO2, H2O, and newly cleaved quartz (001) surfaces in order to understand the mechanisms of carbonation and hydrolysis reactions, which are essential parts of CO2 mineralization. It is shown that CO2 can react with undercoordinated Si and nonbridging O atoms on the newly cleaved quartz surface, leading to formation of CO3 configuration that is fixed on the surface by Si–O bonds. Furthermore, these Si–O bonds can break under hydrolysis reaction, and HCO3 occurs simultaneously. Electron localization function and Bader charge analysis were used to describe the bonding mechanism and charge transfer during the two reaction processes. The result highlights the importance of the intermediate configuration of CO2 γ– in the carbonation reaction process. Furthermore, it confirms the formation of CO3 2– and HCO3 –. We conclude that CO3 2– and HCO3 – in the formation water do not necessarily originate from dissociation of H2CO3, and these anions may accelerate the CO2 mineralization process in the presence of required cations, such as Ca2+, Mg2+, or Fe2+.

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Direct Observation of Carbonate Chemisorption on Barium Titanate Surfaces by Tip‐Enhanced Raman Spectroscopy

Bakhtbidar,

Amaechi,

Dörfler

et al. 2024

Adv Materials Inter

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Surface chemistry significantly influences the physicochemical and functional properties of nanoparticles, thus necessitating the investigation of surfaces, especially when subjected to chemisorption. Seeking a method that delivers both high‐resolution imaging and precise chemical information, tip‐enhanced Raman spectroscopy (TERS) emerges as a critical technique. By the combination of scanning probe microscopy with Raman spectroscopy, TERS effectively addresses the limitations of traditional optical microscopes in the study of nanoparticles. The results provide detailed nanoscale structural insights, shed light on surface chemistry, and enable the detection of Raman‐forbidden modes caused by the substantial electric field at the tip apex (≈3 × 108 V m−1). This electric field plays a crucial role in altering selection rules, thereby broadening the scope of TERS beyond merely detecting Raman modes. By combining topographical with TERS mapping, the presence of a carbonate monolayer on the barium titanate (BaTiO3) nanoparticle surface is unveiled – an observation elusive to common characterization techniques.

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Suppression of surfaces states at cubic perovskite (001) surfaces by CO₂ adsorption

Cited by 14 publications

References 77 publications

Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Ab Initio Molecular Dynamics Study of Carbonation and Hydrolysis Reactions on Cleaved Quartz (001) Surface

Direct Observation of Carbonate Chemisorption on Barium Titanate Surfaces by Tip‐Enhanced Raman Spectroscopy

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Suppression of surfaces states at cubic perovskite (001) surfaces by CO2 adsorption

Cited by 14 publications

References 77 publications

Low-Temperature CO2 Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Low-Temperature CO2 Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Ab Initio Molecular Dynamics Study of Carbonation and Hydrolysis Reactions on Cleaved Quartz (001) Surface

Direct Observation of Carbonate Chemisorption on Barium Titanate Surfaces by Tip‐Enhanced Raman Spectroscopy

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Product

Resources

About

Suppression of surfaces states at cubic perovskite (001) surfaces by CO₂ adsorption

Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions

Low-Temperature CO₂ Thermal Reduction to Graphitic and Diamond-like Carbons Using Perovskite-Type Titanium Nanoceramics by Quasi-High-Pressure Reactions