Chirality of molecular nanostructures on surfaces via molecular assembly and reaction: manifestation and control

Xu, Ying; Duan, Jun-Jie; Yi, Zhen-Yu; Zhang, Kexin; Chen, Ting; Wang, Dong

doi:10.1016/j.surfrep.2021.100531

Cited by 34 publications

(41 citation statements)

References 217 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The electronic state of the transition metal dramatically changes upon alloying with the simple metal. The dominant effect is increase in the d-band filling and, as a consequence, an effective downshift of the d-band center with respect to the Fermi level [ 2 , 9 ]. The latter (electronic effect), along with the transformation of the atomic structure/morphology of the substrate (steric effect) has a significant impact on the molecular adsorption and conversion.…”

Section: Resultsmentioning

confidence: 99%

“…Another alloy as an efficient catalyst in hydrocarbon and carbon monoxide conversion is molybdenum nitride, featuring, for instance, high activity for selective oxidation of methane into alcohols [ 7 , 8 ]. As a demand of automotive exhaust reduction much attention is devoted to the studies of catalytic NO + CO conversion [ 9 ]. In this regard, it is shown, for example, that along with the noble metals—such as Rh, Pt, Pd, and Ir—the tungsten and molybdenum carbides may also be active catalysts for automotive exhaust neutralization [ 10 , 11 ].…”

Section: Introductionmentioning

confidence: 99%

“…Despite of quite extensive research in this field, there are lack of studies of the alloys containing metals of the center of the transition row (d5) with the sp-metals, such as, for instance, W or Mo with Al. At the same time, due to the specific electronic properties of half-filled d-band, and the excess of free charge in such a metal like Al, the d-sp hybridization would shift the center of the d-band down with respect to Fermi level, thus increasing its filling and, as a consequence, enhancing catalytic activity [ 9 ]. In line with this assumption are the previous results of increase in CO catalytic oxidation activity on Mo(110) upon alloying with boron, the element which is isoelectronic to Al [ 12 ].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Preparation of Aluminum–Molybdenum Alloy Thin Film Oxide and Study of Molecular CO + NO Conversion on Its Surface

et al. 2022

View full text Add to dashboard Cite

Adsorption and interaction of carbon monoxide (CO) and nitric oxide (NO) molecules on the surface of bare Al-Mo(110) system and on that obtained by its in situ oxidation have been studied in ultra-high vacuum (base pressure: ca. 10−8 Pa) by means of Auger and X-ray photoelectron spectroscopy (AES, XPS), low energy electron diffraction (LEED), reflection–absorption infrared and thermal desorption spectroscopy (RAIRS, TDS), and by the work function measurements. In order to achieve the Al-Mo(110) alloy the thin aluminum film of a few monolayers thick was in situ deposited onto the Mo(110) crystal and then annealed at 800 K. As a result of Al atoms diffusion into the Mo(110) subsurface region and the chemical reaction, the surface alloy of a hexagonal atomic symmetry corresponding to Al2Mo alloy is formed. The feature of thus formed surface alloy regarding molecular adsorption is that, unlike the bare Mo(110) and Al(111) substrates, on which both CO and NO dissociate, adsorption on the alloy surface is non-dissociative. Moreover, adsorption of carbon monoxide dramatically changes the state of pre-adsorbed NO molecules, displacing them to higher-coordinated adsorption sites and simultaneously tilting their molecular axis closer to the surface plane. After annealing of this coadsorbed system up to 320 K the (CO + NO → CO2 + N) reaction takes place resulting in carbon dioxide desorption into the gas phase and nitriding of the substrate. Such an enhancement of catalytic activity of Mo(110) upon alloying with Al is attributed to surface reconstruction resulting in appearance of new adsorption/reaction centers at the Al/Mo interface (steric effect), as well as to the Mo d-band filling upon alloying (electronic effect). Catalytic activity mounts further when the Al-Mo(110) is in situ oxidized. The obtained Al-Mo(110)-O ternary system is a prototype of a metal/oxide model catalysts featuring the metal oxides and the metal/oxide perimeter interfaces as a the most active reaction sites. As such, this type of low-cost metal alloy oxide models precious metal containing catalysts and can be viewed as a potential substitute to them.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Preparation of Aluminum–Molybdenum Alloy Thin Film Oxide and Study of Molecular CO + NO Conversion on Its Surface

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The understanding of chirality at solid surfaces is of ever-growing importance, and an increasing number of studies have been reported over the years to shed light on the fundamentals and practices in achieving chiral surfaces with definite enantioselectivity (Gellman, 2010;Zaera, 2017;Albano et al, 2020;Xu et al, 2021). As a matter of fact, chirality can be observed or provided to achiral surfaces taking advantage of several options spanning from the addition of chiral modifiers (Zaera, 2008), the adsorbing of chiral molecules at ultra-high vacuum (Costa et al, 2015), or from liquid phase (Huang et al, 2003), or even by self-assembly of achiral molecules that form chiral domains thanks to the surface dimensional constraints (Tao and Bernasek, 2005).…”

Section: Introductionmentioning

confidence: 99%

Seeding Chiral Ensembles of Prolinated Porphyrin Derivatives on Glass Surface: Simple and Rapid Access to Chiral Porphyrin Films

et al. 2022

View full text Add to dashboard Cite

An easy and fast method to achieve chiral porphyrin films on glass is herein reported. The on-surface formation of organized supramolecular architectures with distinctive and remarkable chiroptical features strictly depends on the macrocycles used, the solvent chosen for the casting deposition, and most importantly, on the roughness of the glass slide. Dynamic light scattering studies performed on 10−4–10−6 M porphyrin solutions revealed the presence of small porphyrin aggregates, whose size and number increase depending on the initial concentration. Once transferred on surface, these protoaggregates act as nucleation seeds for the following, self-assembling into larger structures upon solvent evaporation, with a process driven by a fine balance between intermolecular and molecule–substrate interactions. The described method represents a straightforward way to fabricate porphyrin-based chiral surfaces onto a transparent and economic substrate in few minutes. The results obtained can be particularly promising for the development of sensors based on stereoselective optical active films, targeting the detection of chiral analytes of practical relevance, such as the so-called emerging pollutants released in the environment from agrochemical, food, and pharmaceutical manufacturing.

show abstract

“…In particular, double hydrogen bonds between carboxyl groups, which are stronger than single hydrogen bonds, are widely used in the construction of stable supramolecular structures. − The self-assembly of various tricarboxylic acid molecules with inflexible structures has been studied, which often shows the formation of hexagonal networks. − However, conformationally flexible carboxylic acid molecules, which have a 2D chirality when limited to solid surfaces, have rarely been investigated. The 2D chirality of the precursor can steer the self-assembled structures, − which has great importance for the fabrication of supramolecular functional nanostructures …”

Section: Introductionsmentioning

confidence: 99%

Deprotonation-Induced Phase Transitions in the Self-Assembled Structure of Prochiral Carboxyl Derivatives

et al. 2022

View full text Add to dashboard Cite

Controlling the self-assembly of molecules on solid surfaces is of great importance for creating new functional nanostructures. In this work, phase transitions in the self-assembled structure of the 1,3,5-tris(3-carboxyphenyl)benzene (mTCPB) molecule on the Ag(111) surface at different annealing temperatures are characterized by ultrahigh vacuum scanning tunneling microscopy, which reflects the different deprotonation levels of the mTCPB molecule. We also demonstrate that the two-dimensional chirality of the precursor is a powerful tool for steering the supramolecular structures on surfaces.

show abstract

Chirality of molecular nanostructures on surfaces via molecular assembly and reaction: manifestation and control

Cited by 34 publications

References 217 publications

Preparation of Aluminum–Molybdenum Alloy Thin Film Oxide and Study of Molecular CO + NO Conversion on Its Surface

Preparation of Aluminum–Molybdenum Alloy Thin Film Oxide and Study of Molecular CO + NO Conversion on Its Surface

Seeding Chiral Ensembles of Prolinated Porphyrin Derivatives on Glass Surface: Simple and Rapid Access to Chiral Porphyrin Films

Deprotonation-Induced Phase Transitions in the Self-Assembled Structure of Prochiral Carboxyl Derivatives

Contact Info

Product

Resources

About