Water effect on band alignment of GaP: A theoretical insight into pyridinium catalyzed CO 2 reduction

Fan, Xue-Ting; Jia, Mei; Lee, Ming-Hsien; Cheng, Jun

doi:10.1016/j.jechem.2017.03.002

Cited by 8 publications

(11 citation statements)

References 46 publications

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“…The anatase TiO 2 (101), ( 001) and (100) surfaces were modelled with 3 × 1, 4 × 4 and 3 × 1 supercells in xy dimensions, respectively. To give an accurate description of the thickness of the TiO 2 slab, a critical parameter affecting the water adsorption state, [52][53][54][55] the dependence of electrostatic potential on the slab thickness was studied. We calculated the electrostatic potentials of anatase TiO 2 surfaces with different atomic layers and investigated the convergence of the electrostatic potential difference (DV, the difference in average electrostatic potentials between the solid and vacuum phases) against the slab thickness.…”

Section: Model Systemsmentioning

confidence: 99%

Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Sun

Cheng

2023

J. Mater. Chem. A

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Section: Model Systemsmentioning

confidence: 99%

Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Sun

Cheng

2023

J. Mater. Chem. A

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“…Therefore, we investigated the solvation effect on band edge positions of GaP. The absolute positions of the bare GaP(110) surface and the one ML water adsorbed GaP(110) surface in vacuum can be calculated by referencing the HOMO and the LUMO to the vacuum level, and they can be converted into the SHE by subtracting the absolute SHE potential of 4.44 V. Note that the 1 ML water adsorbed GaP(110) surface was modeled by including 1 ML of half-dissociated water molecules on the bare GaP(110) slab (as shown in Figure a), which was found to be the most stable adsorption state. , The results using different density functionals are exhibited in Table S1. The CBM is 0.3 V more positive, while the VBM is 0.4 V more negative at the generalized gradient approximation (GGA) level than those with the hybrid functional HSE06.…”

Section: Resultsmentioning

confidence: 99%

“…We then performed molecular dynamics of the GaP(110)/water interface. Because the band edge positions were found to be strongly influenced by the adsorption states of the water molecules at the semiconductor/water interfaces, , and the kinetics of water dissociation/recombination processes at the GaP(110)/water interface were found to be slow, the molecular dynamics of the GaP(110)/water interface was started from the initial configuration in which the adsorbed water molecules are half-dissociated (as shown in Figure c). We calculated the band edge positions of the GaP(110)/water interface following the procedure described in the Methods.…”

Section: Resultsmentioning

confidence: 99%

“…Please note that the CO 2 reduction reactions occur at the semiconductor/water interface. As has been found in recent studies, water can have a significant effect on the band alignment of semiconductors. − Thus, neglecting the solvation effect may affect the determination of the photocatalytic activities of photoelectrodes. The same group reported later a more reasonable CBM calculated by including a full monolayer (ML) of half-dissociated water molecules adsorbed on the GaP(110) slab model, which shift up the CBM by 0.8 V .…”

Section: Introductionmentioning

confidence: 98%

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Aligning Electronic Energy Levels in Pyridine-Assisted CO₂ Activation at the GaP(110)/Water Interface Using Ab Initio Molecular Dynamics

2022

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Photoelectrochemical CO 2 reduction has attracted considerable attention as a route to convert CO 2 into value-added products. Pyridine (Py)-catalyzed CO 2 reduction on a GaP photoelectrode has been shown to be a promising photoelectrochemical system to produce methanol under the underpotential condition. However, whether the dramatic decrease in overpotential can be attributed to the CO 2 activation by the formation of the zwitterionic complex PyCO 2 is currently under debate. Because the alignment between the band edge positions of photoelectrodes and the redox potentials of species determines the desired redox reactions, calculations have been performed to evaluate the band edge positions of GaP and the redox potentials of relevant reactions. In these works, the water effect has been either neglected or approximated by using the dielectric continuum or a few explicit water molecules, which may not be enough to determine the accurate energy level alignment in realistic chemical environments. Moreover, calculations performed in conventional implicit solvation models suggested that PyCO 2 is unstable in homogeneous aqueous, while the bonding interactions between CO 2 and N species have been experimentally detected. Thus, we performed ab initio molecular dynamics to investigate the band alignment of GaP, as well as the stability and the reducibility of PyCO 2 in more realistic chemical environments. Our results showed that the solvation effect and the pyridine adsorption could shift up the band edge positions of GaP significantly, and neglecting such effects could result in a serious underestimation of the activity of the photocatalysts. More importantly, we found that the interaction between pyridine and CO 2 at the GaP(110)/water interface is strong due to the synergetic stabilization effect, which leads to an about 0.6 V less negative redox potential of PyCO 2 /PyCO 2 − than that of CO 2 /CO 2 − in the homogeneous aqueous. Furthermore, we compared the redox potential of PyCO 2 /PyCO 2 − at the GaP(110)/water interface with the conduction band minimum of GaP, which showed that the reduction of the adsorbed PyCO 2 is thermodynamically feasible. Our results suggested that the CO 2 activation by the formation of PyCO 2 at the GaP(110)/water interface could be responsible for the low overpotential. This work provides valuable insights into the mechanism of pyridine-catalyzed CO 2 reduction on GaP and could pave the way for the development of efficient catalysts for CO 2 reduction.

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“…In the last few years, the greenhouse emission has become a great concern for the whole scientific community as it affected the climate badly. As from the results, various methods have been proposed to separate, capture, store and detect greenhouse gases [1][2][3], with a significant contribution due to CO2 in global warming [4,5]. Here, the key issues are predicting / proposing new materials as efficient to CO2, capturing, storing and/or modifying materials [6,7].…”

Section: Introductionmentioning

confidence: 99%

Realization of Switching Mechanism of CO2 by Alkaline Adatoms on g-B4N3 Surface

Kansara

Gupta

Sonvane

et al. 2019

Springer Proceedings in Physics

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The adsorption and desorption of carbon dioxide (CO2) molecule by alkaline earth metal (AEM) (Mg +2 , Ca +2 , Sr +2 and Ba +2 ) functionalized on graphitic boron nitride (g-B4N3) nanosheet have been analyzed by using density functional theory (DFT) approach includes long-range correlation (DFT+D). This method has been implemented in such a way to understand the switchable or capture/release mechanism of CO2 molecule by computing the electron mobility, electronic properties, charge accumulation, charge transfer (e -) and adsorption energy (Kcal/mol). The g-B4N3 nanosheet yields high carrier mobility (8020 cm 2 V -1 s -1 ) at 300 K. The positive alkaline earth adatoms on the nanosheet of g-B4N3 has been provided external energy to do the capture/release process of greenhouse gas CO2. Here, Mg positive ion work as adatom which confirms physisorption while others show chemisorption behaviors. Therefore, due to the weak absorption of CO2, it makes possible to discharge from the g-B4N3 nanosheet and shows instantaneous switching mechanism. Briefly, the negatively charged g-B4N3 nanosheets are highly sensitive for CO2.

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Water effect on band alignment of GaP: A theoretical insight into pyridinium catalyzed CO 2 reduction

Cited by 8 publications

References 46 publications

Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Aligning Electronic Energy Levels in Pyridine-Assisted CO₂ Activation at the GaP(110)/Water Interface Using Ab Initio Molecular Dynamics

Realization of Switching Mechanism of CO2 by Alkaline Adatoms on g-B4N3 Surface

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Water effect on band alignment of GaP: A theoretical insight into pyridinium catalyzed CO 2 reduction

Cited by 8 publications

References 46 publications

Theoretical investigation on water adsorption conformations at aqueous anatase TiO2/water interfaces

Theoretical investigation on water adsorption conformations at aqueous anatase TiO2/water interfaces

Aligning Electronic Energy Levels in Pyridine-Assisted CO2 Activation at the GaP(110)/Water Interface Using Ab Initio Molecular Dynamics

Realization of Switching Mechanism of CO2 by Alkaline Adatoms on g-B4N3 Surface

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Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Theoretical investigation on water adsorption conformations at aqueous anatase TiO₂/water interfaces

Aligning Electronic Energy Levels in Pyridine-Assisted CO₂ Activation at the GaP(110)/Water Interface Using Ab Initio Molecular Dynamics