The Effect of Nano Confinement on the C–H Activation and its Corresponding Structure-Activity Relationship

Shao, Jianghua; Yuan, Linghua; Hu, Xingbang; Wu, Youting; Zhang, Zhibing

doi:10.1038/srep07225

Cited by 15 publications

(13 citation statements)

References 73 publications

(203 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As shown in Figs S5 and S6, *CH 4 dehydrogenation are as follows: *CH 4 → *CH 3 → *CH 2 → *CH → *C, which is in accordance with the previous studies of CH 4 dehydrogenation on different metals and alloys using DFT 31 32 33 34 35 36 37 38 39 . Table S1 shows the adsorption parameters of *CH 4 , *CH 3 , *CH 2 , *CH and *C on a Cu site.…”

Section: Resultssupporting

confidence: 90%

Efficient Synthesis of Ethanol from CH4 and Syngas on a Cu-Co/TiO2 Catalyst Using a Stepwise Reactor

Zuo

Peng

Huang

2016

Sci Rep

View full text Add to dashboard Cite

Ethanol synthesis from CH4 and syngas on a Cu-Co/TiO2 catalyst is studied using experiments, density functional theory (DFT) and microkinetic modelling. The experimental results indicate that the active sites of ethanol synthesis from CH4 and syngas are Cu and CoO, over which the ethanol selectivity is approximately 98.30% in a continuous stepwise reactor. DFT and microkinetic modelling results show that *CH3 is the most abundant species and can be formed from *CH4 dehydrogenation or through the process of *CO hydrogenation. Next, the insertion of *CO into *CH3 forms *CH3CO. Finally, ethanol is formed through *CH3CO and *CH3COH hydrogenation. According to our results, small particles of metallic Cu and CoO as well as a strongly synergistic effect between metallic Cu and CoO are beneficial for ethanol synthesis from CH4 and syngas on a Cu-Co/TiO2 catalyst.

show abstract

Section: Resultssupporting

confidence: 90%

Efficient Synthesis of Ethanol from CH4 and Syngas on a Cu-Co/TiO2 Catalyst Using a Stepwise Reactor

Zuo

Peng

Huang

2016

Sci Rep

View full text Add to dashboard Cite

show abstract

“…To the best of our knowledge and despite an increasing number of excellent theoretical contributions, − the only reported preparative, noncatalyzed, organic chemical reaction performed experimentally within narrow carbon nanotubes is the aromatic halogenation reaction, where it was observed that extreme spatial confinement in narrow single-walled carbon nanotubes (SWNTs) directed the site-selective electrophilic attack of the incarcerated aromatic guest reactant and resulted in an enhancement in the formation of the more linear para-regioisomer from 68 to 97%. In this study, we explore the effect of nanoscale confinement in SWNTs on the formation of the products of 1,3-dipolar cycloaddition reactions, a class of bimolecular reactions with two reactants typically of commensurate size and complexity.…”

Section: Introductionmentioning

confidence: 99%

Steric and Electronic Control of 1,3-Dipolar Cycloaddition Reactions in Carbon Nanotube Nanoreactors

et al. 2019

View full text Add to dashboard Cite

The use of single-walled carbon nanotubes as effective nanoreactors for preparative bimolecular reactions has been demonstrated for the first time. We show that the extreme spatial confinement of guest reactant molecules inside host carbon nanotubes increases the regioselectivity for the 1,4-triazole in thermally-initiated azide-alkyne cycloaddition reactions.Through comparison of the internal dimensions of the nanotube and the steric bulk of the reactants, we demonstrate that the formation of the more linear 1,4-regioisomer can be enhanced by up to 55% depending on the extent of spatial restrictions imposed within the nanoreactors. Furthermore, through systematic variation of the substituents in the para-position of the alkyne reactants, we reveal the unexpected influence of the electronic properties of the reactants on the regioselectivity 2 of reactions within nanoreactors, which act to either oppose or promote the preferential formation of the 1,4-regioisomer induced by steric effects, reflecting the unique ability of carbon nanotubes to stabilise the dipole moment of confined reactants. Thus, we show that the observed regioselectivity of azide-alkyne cycloaddition reactions confined within carbon nanotube nanoreactors reflects a subtle interplay between both steric and electronic factors.

show abstract

“…For b-La samples, the position of peak C is intentionally determined by the peak of the sample at 0.5 days of P adsorption in Figure a (132.9 eV), in which we have concluded that this sample is virtually the inner-sphere complexation of HPO 4 2– or H 2 PO 4 – on the surface of La(OH) 3 particles based on previous results. ,, With respect to La@201, a higher binding energy peak C at 134.7 eV is automatically set by the software to complete the data fitting once the positions of peaks A and B are fixed. The higher binding energy of peak C in La@201 than that in b-La suggests a stronger binding affinity of P species with the La(OH) 3 crystals under nanoconfinement, where the exposed crystal facets and the chemical environment could be different. ,− …”

Section: Resultsmentioning

confidence: 99%

Structural Evolution of Lanthanum Hydroxides during Long-Term Phosphate Mitigation: Effect of Nanoconfinement

Zhang

Wang

Gao

et al. 2020

Environ. Sci. Technol.

View full text Add to dashboard Cite

Lanthanum (La)-based materials are effective in removing phosphate (P) from water to prevent eutrophication. Compared to their bulky analogues, La(OH)3 nanoparticles exhibit a higher P removal efficiency and a more stable P removal ability when spatially confined inside the host. Consequently, the understanding of the nanoconfinement effects on the long-term evolution of La–P structures is crucial for their practical use in P sequestration and recycle, which, however, is still missing. Here, we describe an attempt to explore the evolution of La–P structures, the P environment, and the status of La(OH)3 nanoparticles confined in the nanopores of the D201 resin, compared to a nonconfined analogue, over a P adsorption period of 25 days in both simulated wastewater and the real bioeffluent. A combinative use of X-ray diffraction (XRD), cross-polarization nuclear magnetic resonance (CP-NMR), and X-ray photoelectron spectroscopy (XPS) techniques confirms the transition from La–P inner-sphere complexation to the formation of LaPO4·xH2O and finally to LaPO4 in both samples. Interestingly, the rate of structural transformation in the real bioeffluent is substantially reduced. Nevertheless, in both conditions, nanoconfinement results in a much faster rate and larger extent of the structural transition. Moreover, nanoconfinement also facilitates the reverse transformation of stable LaPO4 back to La(OH)3. Our work provides the scientific basis of nanoconfinement for the preferable use of La-based nanocomposites in P mitigation, immobilization, and recycle application.

show abstract

The Effect of Nano Confinement on the C–H Activation and its Corresponding Structure-Activity Relationship

Cited by 15 publications

References 73 publications

Efficient Synthesis of Ethanol from CH4 and Syngas on a Cu-Co/TiO2 Catalyst Using a Stepwise Reactor

Efficient Synthesis of Ethanol from CH4 and Syngas on a Cu-Co/TiO2 Catalyst Using a Stepwise Reactor

Steric and Electronic Control of 1,3-Dipolar Cycloaddition Reactions in Carbon Nanotube Nanoreactors

Structural Evolution of Lanthanum Hydroxides during Long-Term Phosphate Mitigation: Effect of Nanoconfinement

Contact Info

Product

Resources

About