Theoretical studies of a 3D-to-planar structural transition in SinAl5−n+1,0,−1(n = 0–5) clusters

Zhu, Jinzhen; Wang, Beizhou; Li, Jianjun; Chen, Huanwen; Zhang, Wenqing

doi:10.1039/c4ra15955a

Cited by 3 publications

(5 citation statements)

References 44 publications

(56 reference statements)

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“…Therefore, in the present study, a catalyst/Li 2 O 2 /O 2 interfacial model is constructed to simulate catalytic activity in desorption energies of O 2 and Li + for calculating the corresponding charging potential. Our previous studies and other reports we followed showed that the interfacial catalytic model could generate reliable prediction results by comparing them with experimental values for verification. ,,− Based on the first-principles thermodynamic calculations for Li 2 O 2 , the low-energy Li 2 O 2 (0001) and Li 2 O 2 (11̅00) surfaces with O-rich coverage are identified as very possibly exposed structures after discharging, which was later confirmed by Shao-Horn et al Therefore, in our interfacial calculations, two O-rich surfaces (0001) and (11̅00) are exposed in a vacuum to simulate the O 2 gas environment. Therefore, it is of great importance to determine which catalytic surface should directly interact with Li 2 O 2 (0001).…”

Section: Resultssupporting

confidence: 75%

“…The interfacial structures of Li 2 O 2 /catalysts were optimized through the attainment of the smallest lattice mismatch of two solid phases. The detailed procedure of interfacial structure calculations has been elaborately described in our previous paper. ,, The lattice changes are calculated by the following: Here, δ is the lattice mismatch. L 0 is the length of the lattice of the TM of a certain direction.…”

Section: Resultsmentioning

confidence: 99%

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Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery

Zhao

Wang

et al. 2020

ACS Appl. Mater. Interfaces

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The development of active electrocatalysts for enhancing Li2O2 decomposition kinetics plays an important role in reducing the overpotential of Li–O2 batteries. However, a catalytic descriptor is not established due to the difficult characterization of the charge transfer between Li2O2 and the catalyst. Here, we employ first-principles thermodynamic calculations to study the electrocatalytic mechanism of 4d transition metals. We found that charge acceptation and donation capacities of catalysts, defined as surface electron affinity (V SEA) and surface ionic potential (V SIP), take cooperative responsibilities for the activation of Li–O2 bonds and the reduction of desorption barriers of Li+ and O2, respectively. Therefore, we define surface electronegativity V SE (V SE = (V SEA + V SIP)/2), which exhibits a volcano curve with a reduced charge overpotential, as the catalytic descriptor. We identified those catalysts with surface electronegativities of 1.7–2.2 V to have highly catalytic activities in the reduction of the charge overpotential, which are well verified by previous experimental data. The present study opens a wide avenue in the development of high-activity catalysts for interfacial electrocatalysts by an effective descriptor.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery

Zhao

Wang

et al. 2020

ACS Appl. Mater. Interfaces

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“…They found that Liadsorbed sites on B-doped graphene, as the electronwithdrawing center, enhance charge transfer from Li 2 O 2 to the cathode and thus reduce the O 2 evolution barrier. Furthermore, they took surface acidity (defined as the energy change of catalysts with charge transfer) as a descriptor of charge transfer to study the electrocatalytic activity in the charging process [77,80,81]. They elucidated that the O-rich Co 3 O 4 (111) surface with a relatively low surface energy, promoting charge transfer from the Li 2 O 2 particles to the underlying surface, has a high catalytic activity to reduce overpotential and the O 2 evolution barrier [80].…”

Section: Charge Transfermentioning

confidence: 99%

Adsorption-energy-based activity descriptors for electrocatalysts in energy storage applications

Wang

Qiu

Song

et al. 2017

National Science Review

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156

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Energy storage technologies, such as fuel cells, ammonia production and lithium-air batteries, are important strategies for addressing the global challenge of energy crisis and environmental pollution. Taking overpotential as a direct criterion, we illustrate in theory and experiment that the adsorption energies of charged species such as Li + +e − and H + +e − are a central parameter to describe catalytic activities related to electricity-in/electricity-out efficiencies. The essence of catalytic activity is revealed to relate with electronic coupling between catalysts and charged species. Based on adsorption energy, some activity descriptors such as d-band center, e g -electron number and charge-transfer capacity are further defined by electronic properties of catalysts that directly affect interaction between catalysts and charged species. The present review is helpful for understanding the catalytic mechanisms of these electrocatalytic reactions and developing accurate catalytic descriptors, which can be employed to screen high-activity catalysts in future high-throughput calculations and experiments.

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“…To our best knowledge, Si 3 Al 2 is the only reported neutral 18ve‐ptM for heavier group 14 by means of the quantum chemical calculations (the experimentally verified

{SiAl}_{4}^{-}

and SiAl 4 contain the 17 and 16ve, respectively).The presently predicted sixteen neutral ptM systems surely expand the family of 18ve‐ptM to a significantly large extent. Besides, the global ptC in the reported binary or ternary systems (e.g.,

{CAl}_{4}^{2 -}

,c,d, CAl 3 Si ‐ , CAl 3 Ge ‐ , CAl 2 Si 2 , CAl 2

{Ge}_{2}^{}

) are mainly associated with the σ‐type bonding within the skeleton.…”

Section: Resultsmentioning

confidence: 90%

“…Alternatively, the monocharged or neutral species are quite suitable for spectroscopic studies. By replacing one or more Al‐atoms by Si within

{SiAl}_{4}^{2 -}

, the 18ve‐

{Si}_{2} {Al}_{3}^{-}

{Si}_{3} {Al}_{2}^{}

, and Si 4 Al+ have been successfully designed to each contain a global ptSi. Being either neutral or only monocharged, the three molecules are very suitable for spectroscopic characterization.…”

Section: Introductionmentioning

confidence: 99%

New structural motif of 18 valence electron molecules with a planar tetracoordinate heavier group 14 center: Unique stabilization effect of a π‐type skeleton

2017

Int J of Quantum Chemistry

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Proposing new valence electron counting rules and new structural motifs are both very important in chemistry. In this work, we unexpectedly found that by introducing a p-type skeleton YCCY (Y 5 Al/Ga/In/Tl), a total of sixteen novel planar tetracoordinate heavier group 14 species, that is, ptM (M 5 Si/Ge/Sn/Pb) in neutral, can be designed as global minima. The underlying bonding situation contrasts sharply both with the well-known 18ve-ptC and the limited 18ve-ptM, for which there is little multiple bonding character within the skeleton. The fact that each YCCY (Y 5 Al/Ga/ In/Tl) can stabilize all heavier group 14 atoms in a planar tetracoordinate fashion strongly demonstrates the universality of such a p-type skeleton. The present work firmly demonstrates that introducing the p-type ligand skeleton can effectively enrich the planar tetracoordinate chemistry with the heavier group atoms.computation, global minima, heavier group 14 elements, planar tetracoordinate, p-type skeleton 1 | I N TR ODU C TI ON Making molecules that have seemingly strange structures are always attractive to both experimentalists and theoreticians. One nice example is the planar tetracoordinate carbon (ptC), [1] which violates the traditional tetrahedral carbon skeleton-one of the most important concepts in the organic chemistry. The ptC concept was initially raised in 1968, [2] computationally rationalized in 1970, [3] and computationally confirmed as an energy minimum in 1976. [4] Over the past nearly 50 years, the ptC concept has been effectively transferred to diverse hypercoordiante systems including the cluster-assembled [5] and extended ones [6] that could have potential applications in materials science.In chemistry, electron counting rules are very important in describing the stability of atoms and compounds. The well-known examples include the octet rule [7] for an atom, the 18-electron rule for transition metal-based compounds, [8] and the Wade-Mingos rule for polyhedral borane clusters. [9] Gratifyingly, in the ptC field, there is also a very useful electron counting rule, also namely the 18-electron rule. In 1991, Boldyrev and Schleyer studied a series of penta-atomic molecules and found that all these species possess the 18 valence electrons to favor the effective ligandligand bonding around a planar tetracoordinate center. [10] Surely, the 18ve-rule in planar tetracoordiante chemistry is quite different from that in transition metal compounds. Ever since then, the 18ve-rule has been shown quite effective in designing various planar tetracoordiante [11] and even planar pentacoordiante molecules for the first-row elements. [12]

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Theoretical studies of a 3D-to-planar structural transition in Si_nAl_5−n^+1,0,−1(n = 0–5) clusters

Abstract: A novel ptC structure C2Al3− which is more stable in energy than the experimentally observed CAl42−.was firstly predicted The C2Al3− may become a building block to assembly some larger supermolecule containing multiple phC.

Cited by 3 publications

References 44 publications

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery

Adsorption-energy-based activity descriptors for electrocatalysts in energy storage applications

New structural motif of 18 valence electron molecules with a planar tetracoordinate heavier group 14 center: Unique stabilization effect of a π‐type skeleton

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Theoretical studies of a 3D-to-planar structural transition in SinAl5−n+1,0,−1(n = 0–5) clusters

Abstract: A novel ptC structure C2Al3− which is more stable in energy than the experimentally observed CAl42−.was firstly predicted The C2Al3− may become a building block to assembly some larger supermolecule containing multiple phC.

Cited by 3 publications

References 44 publications

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O2 Battery

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O2 Battery

Adsorption-energy-based activity descriptors for electrocatalysts in energy storage applications

New structural motif of 18 valence electron molecules with a planar tetracoordinate heavier group 14 center: Unique stabilization effect of a π‐type skeleton

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Theoretical studies of a 3D-to-planar structural transition in Si_nAl_5−n^+1,0,−1(n = 0–5) clusters

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery

Surface Electronegativity as an Activity Descriptor to Screen Oxygen Evolution Reaction Catalysts of Li–O₂ Battery