Adsorption Of Molecules Research Articles

Ultrasmall copper-metal organic framework (Cu-MOF) quantum dots decorated on waste derived biochar for enhanced removal of emerging contaminants: Synergistic effect and mechanistic insight

This study proposes a novel one-pot hydrothermal impregnation strategy for surface decoration of waste derived pisum sativum biochar with zero‒dimensional Cu‒MOF Quantum dots (PBC‒HK), with an average particle size of 5.67 nm, for synergistic removal of an emerging sulfur containing drug pantoprazole (PTZ) and Basic Blue 26 (VB) dye within 80 min and 50 min of visible-light exposure, respectively. The designed Integrated Photocatalytic Adsorbent (IPA) presented an enhanced PTZ removal efficiency of 95.23% with a catalyst loading of 0.24 g/L and initial PTZ conc. 30 mg/L at pH 7, within 80 min via synergistic adsorption and photodegradation under visible-light exposure. While, on the other hand, 96.31% VB removal efficiency was obtained in 50 min with a catalyst dosage of 0.20 g/L, initial VB conc. 60 mg/L at pH 7 under similar irradiation conditions. An in-depth analysis of the synergistic adsorption and photocatalysis mechanism resulting in the shortened time for the removal of contaminants in the synergistic integrated model has been performed by outlining the various advantageous attributes of this strategy. The first-order degradation rate constant for PTZ was found to be 0.04846 min−1 and 0.04370 min−1 for PTZ and VB, respectively. Adsorption of contaminant molecules on the biochar (PS‒BC) surface can facilitate photodegradation by accelerating the kinetics, and photodegradation promotes regeneration of adsorption sites, contributing to an overall reduction in operation time for removal of contaminants. Besides enhancing the adsorption of targeted pollutants, the carbon matrix of IPAs serves as a surface for adsorption of intermediates of degradation, thereby minimizing the risk of secondary pollution. The photogenerated holes present in the VB is responsible for the generation of •OH radicals. While, the photogenerated electrons present in the CB are captured by Cu2+ of the MOF metal center, reducing it to Cu+, which is subsequently oxidized to produce additional •OH species in the aqueous medium. This process leads to effective charge separation of the photogenerated charge carriers and minimizes the probability of charge recombination as evident from photoluminescence (PL) analysis. Meanwhile, PL studies, EPR and radical trapping experiments indicate the predominant role of •OH radicals in the removal mechanism of PTZ and VB. The investigation of the degradation reaction intermediates was confirmed by HR‒LCMS, on the basis of which the plausible degradation pathway was elucidated in detail. Moreover, effects of pH, inorganic salts, other organic compounds and humic acid concentration have been investigated in detail. The environmental impact of the proposed method was comprehensively evaluated by ICP-OES analysis and TOC and COD removal studies. Furthermore, the economic feasibility and the cost-effectiveness of the catalyst was assessed to address the potential for large scale commercialization. Notably, this research not only demonstrates a rational design strategy for the utilization of solid waste into treasure via the fabrication of IPAs based on MOF Quantum dots (QDs) and waste-derived biochar, but also provides a practical solution for real wastewater treatment systems for broader industrial applications.

Verbena officinalis (VO) leaf extract as an anti-corrosion inhibitor for carbon steel in acidic environment

In the present work, Verbena Officinalis (VO) leaf extract was used as potential corrosion inhibitor for the corrosion of carbon steel (CS) in 0.5 M H2SO4 medium. Further, the corrosion inhibiting nature of VO leaf extract towards the CS was evaluated using mass loss (ML), potentiodynamic polarization (PDP), electrical impedance spectroscopy (EIS) and surface morphological analyses using atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS) techniques. Calculation of activation energy Ea∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\left( {{\ ext{E}}_{{\ ext{a}}}^{*} } \\right)$$\\end{document} using Arrhenius equation shows the increase in activation energy when adding the VO leaf extract in 0.5 M H2SO4 medium and the maximum activation energy (Ea∗\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{E}}_{{\ ext{a}}}^{*}$$\\end{document} = 49.9 kJ mol−1) was observed for 1000 mg L−1 VO leaf extract in acid medium. The negative free energy values suggested the spontaneous and the stability of the adsorbed layer of VO leaf extract on the CS surface. Using EIS measurements, high percent inhibitory effectiveness of 91.1% for 1000 ppm solutions was achieved. With an increase in VO leaf extract dose, the double layer capacitance (Cdl) values fall while the values of charge transfer (Rct) increase. This showed that a protective layer of VO leaf extract on CS surface was formed. The polarization curves showed that the VO leaf extract acts as a mixed-type inhibitor. It is discovered that the adsorption of VO leaf extract molecules adhering to the CS surface followed the Langmuir isotherm. The anti-corrosion action of VO leaf extract is fully demonstrated by some surface techniques.

Anchoring Atomically Precise Chiral Bismuth Oxido Nanoclusters on Gold: The Role of Amino Acid Linkers.

The adsorption of chiral molecules onto metallic surfaces triggers electron spin polarization at the interface, paving the way for applications in chiral opto-spintronics. However, the spin effects sensitively depend on the binding and ordering of the chiral species on surfaces. This study explores the adsorption of chiral thioether-functionalized atomically precise bismuth oxido nanoclusters (BiO-NCs) on gold (Au) surfaces, extending the conventional approach of using thiol-containing molecules and complexes to nanoclusters. Starting from the precursor [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (A), chiral BiO-NCs were synthesized by substituting the nitrates with N-(tert-butoxycarbonyl)-l-methionine (Boc-l-Met-O-) ligands to obtain [Bi38O45(Boc-l-Met-O)24] (2). The full exchange of nitrate by the Boc-l-methionine ligand was demonstrated by powder X-ray diffractograms, dynamic light scattering, electrospray ionization mass spectrometry, nuclear magnetic resonance, infrared, circular dichroism, and X-ray photoelectron spectroscopy. Compared to previously reported [Bi38O45(Boc-l-Phe-O)24(dmso)9] (1), BiO-NC 2 shows differences in the growth mode on a Au surface as revealed by scanning electron microscopy, wherefore a stronger binding of BiO-NC 2 is assumed. Anchoring of BiO-NC 2 to the Au surface through thioether groups induced a discernible change in the optical response of the Au surface analyzed by spectroscopic ellipsometry (SE). From the numerical modeling of the SE parameters, a layer thickness of ∼2 nm, corresponding to a monolayer of BiO-NC 2, was estimated for the samples prepared by dip coating. Thus, strong adsorption of BiO-NC 2 to the Au surface is concluded, which is an essential prerequisite for chiral-induced interface spin polarization.

Applicability of cationic surfactants, anionic surfactants, and nonionic surfactants as foaming agents for foamed concrete: surface activity, foamability, and interaction with cement

Selecting the appropriate surfactant as a foaming agent is crucial in the production of foamed concrete. In this study, multiple technological approaches were employed for the investigation of the effect of three different types of surfactants as foaming agents; the approaches included surface tension measurement, zeta potential analysis, spectrophotometry, and nanoindentation. The results showed that the surface activity, solution viscosity, and environmental pH all influenced the generation and stability of foam in foaming agents. The adsorption process of surfactants onto cement particles was complex and could be effectively explained using the double-layer theory. The adsorption of anionic surfactant molecules on cement particles significantly altered the zeta potential, up to −17 mV, with an adsorption efficiency over 10 times greater than that of cationic surfactants and more than 5 times greater than that of nonionic surfactants. Furthermore, after cement hardening, the mechanical properties of the resulting pores were notably improved due to the presence of adsorbed anionic surfactants, and the maximum compressive strength could exceed 10 MPa.

Methanol electrooxidation performance of nickel-modified polyaniline thin films for direct methanol fuel cells

A metal–organic composite thin film composed of polyaniline (PANI) and Ni was prepared and characterized for methanol electrooxidation reaction. First, PANI thin films were electrodeposited on a fluorine-doped tin oxide (FTO) coated glass support in an aqueous acidic solution. Subsequently, the polymer film was modified with Ni particles (FTO/PANI-Ni) by chronoamperometric (CA) technique. The composite film was characterized by structural, morphological and electrocatalytic analyses. X-ray diffraction (XRD) results confirmed the crystallization of Ni according to the cubic structure. Scanning electron microscopy (SEM) images showed that the Ni nanoparticles were uniformly dispersed on the PANI surface. The electrocatalytic performance of the FTO/PANI-Ni composite electrode for the methanol electrooxidation reaction was investigated in 0.5 M KOH solution containing methanol using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA) techniques. The effects of temperature and methanol concentration on the methanol electrooxidation performance were also studied. The modified composite catalyst exhibited an electrochemically active surface area of 0.5235 cm2. The presence of Ni nanoparticles on the polymer surface promoted the adsorption of methanol molecules and facilitated the oxidation process, leading to higher current densities and better overall performance. The maximum current density was 14 mA cm-2 and the electrode maintain 68 % of its initial activity even after 200 cycles, indicating that the FTO/PANI-Ni electrode exhibited good stability. The high methanol oxidation performance of the composite electrode was associated with large real surface area, a possible synergistic effect between the polymer moleucles and Ni particles as well as high intrinsic activity of Ni for this process.

Acetylene and Ethylene Adsorption during Floating Fe Catalyst Formation at the Onset of Carbon Nanotube Growth and the Effect of Sulfur Poisoning: a DFT Study.

Here, we investigated the adsorption of acetylene and ethylene on iron clusters and nanoparticles, which is a crucial aspect in the nascent phase of carbon nanotube growth by floating catalyst chemical vapor deposition (FCCVD). The effect of sulfur on adsorption was also studied due to its indispensable role in the process and its commonly known impact on metal catalyst poisoning. We performed systematic density functional theory (DFT) computations, considering numerous adsorption configurations and iron particles of various sizes (Fen, n = 3-10, 13, 55). We found that acetylene binds significantly more strongly than ethylene and prefers different adsorption sites. The presence of sulfur decreased the adsorption strength only in the immediate proximity of the adsorbate, suggesting that the effect of sulfur is mainly of steric origin while electronic effects play only a minor role. Higher sulfur coverage of the catalyst surface significantly weakened the binding of acetylene or ethylene. To further investigate this interaction, Bader's atoms in molecules (AIM) analysis and charge density difference (CDD) were used, which showed electron transfer from iron clusters or nanoparticles to the adsorbate molecules. The charge transfer exhibited a decreasing trend as sulfur coverage increased. These results can also contribute to the understanding of other iron-based catalytic processes involving hydrocarbons and sulfur, such as the Fischer-Tropsch synthesis.

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Tuning Preferential Molecular Adsorption and Self-Assembled Molecular Network Formation at the Liquid–Solid Interface: The Impact of Annealing and Confinement

Fast Outer-Sphere Electron Transfer and High Specific Capacitance at Covalently Modified Carbon Electrodes.

Carbon electrodes typically display sluggish electron transfer kinetics due to the adsorption of adventitious molecules that effectively insulate the surface. Here, we describe a method for rendering graphitic carbon electrodes permanently hydrophilic by functionalization with 4-(diazonium)benzenesulfonic acid. In aqueous electrolytes, these hydrophilic carbon electrodes exhibit metal-like specific capacitance (∼40 μF/cm2) as measured by cyclic voltammetry, suggesting a change in the double-layer structure at the carbon surface. Additionally, the modified electrodes show fast charge transfer kinetics to outer-sphere one-electron redox couples such as ferro-/ferricyanide as well as improved electron transfer kinetics in alkaline aqueous redox flow batteries.

Enhanced activity in industrial hydrogen evolution reaction on NiS/NiCoP by sulfur vacancy coupled with transition metal doping

Ni-based chalcogenide catalysts show the weak H2O molecule adsorption and sluggish kinetics, restricting their industrial hydrogen evolution reaction (HER) in a wide pH range. Herein, a controllable fabrication strategy of NiS/NiCoP nanoparticles by simultaneously constructing sulfur vacancies and introducing the heterometallic atoms (Zn, Fe, Mn) (M-NiCoSP-Sv) is proposed. The numerous uncoordinated surface Ni centers generated by sulfur vacancies are beneficial for cleaving the HO–H bond of H2O molecule, while S sites at Sv-NiS side and P sites at Zn-NiCoP side with rich electron aggregation are used as H2-evolution centers, synergistically facilitating HER kinetics over a wide pH range. As respected, Zn-NiCoSP-Sv exhibits excellent durability and outstanding HER activity such as 41, 78 and 34 mV of 10 mA cm–2 in alkaline, neutral and acidic electrolytes, respectively. And at the industrial current density, Zn-NiCoSP-Sv also possesses outstanding HER activity and stability. This work reveals a strategy for activating NiS-based catalyst to cleave H2O and optimize Gibbs free energy of H* by vacancy and doping co-engineering.

Review of the Interfacial Structure and Properties of Surfactants in Petroleum Production and Geological Storage Systems from a Molecular Scale Perspective.

Surfactants play a crucial role in tertiary oil recovery by reducing the interfacial tension between immiscible phases, altering surface wettability, and improving foam film stability. Oil reservoirs have high temperatures and high pressures, making it difficult and hazardous to conduct lab experiments. In this context, molecular dynamics (MD) simulation is a valuable tool for complementing experiments. It can effectively study the microscopic behaviors (such as diffusion, adsorption, and aggregation) of the surfactant molecules in the pore fluids and predict the thermodynamics and kinetics of these systems with a high degree of accuracy. MD simulation also overcomes the limitations of traditional experiments, which often lack the necessary temporal-spatial resolution. Comparing simulated results with experimental data can provide a comprehensive explanation from a microscopic standpoint. This article reviews the state-of-the-art MD simulations of surfactant adsorption and resulting interfacial properties at gas/oil-water interfaces. Initially, the article discusses interfacial properties and methods for evaluating surfactant-formed monolayers, considering variations in interfacial concentration, molecular structure of the surfactants, and synergistic effect of surfactant mixtures. Then, it covers methods for characterizing microstructure at various interfaces and the evolution process of the monolayers' packing state as a function of interfacial concentration and the surfactants' molecular structure. Next, it examines the interactions between surfactants and the aqueous phase, focusing on headgroup solvation and counterion condensation. Finally, it analyzes the influence of hydrophobic phase molecular composition on interactions between surfactants and the hydrophobic phase. This review deepened our understanding of the micro-level mechanisms of oil displacement by surfactants and is beneficial for screening and designing surfactants for oil field applications.

Electrochemical deposition combined with high-temperature molecular sieve adsorption strategy: Efficient removal of key fission element yttrium for purification of radioactive molten salts

In order to realize energy cost savings in waste salt recycling and electrolysis processes during the nuclear fuel cycle, this paper presents a novel approach for the purification of waste molten salt by employing molecular sieves to absorb excess fission products selectively. The method is founded on the principles of electrolytic refining to achieve sustainable development of reprocessing. In this study, a systematic investigation of the electrochemical reduction/oxidation processes of Y(III)/In(III) was performed on electrode, as well as the electrode reaction of Y(III) on an In electrode at 773 K. Constant-current electrolysis produced an extraction rate of 93.11 % for Y(III) on the In electrode. In order to improve the current efficiency, greatly save the processing cost, and realize the sustainable development of dry post-processing. Subsequently, the waste molten salt environment following electrolysis was simulated, and the fission product was effectively adsorbed utilizing 5A molecular sieves, resulting in a yttrium removal rate of up to 99.94 %. This process not only significantly reduces the cost of electrolysis but also enhances the removal efficiency of target nuclides. The study examined the molten salt adsorption mechanism of molecular sieve, determining the primary adsorption mechanism to be chemical one (ion exchange), through the application of pseudo-first-order, pseudo-second-order, and Weber-Morris kinetic models for re-evaluation.

The molecular binding sequence transformation of soil organic matter and biochar dissolved black carbon antagonizes the transport of 2,4,6-trichlorophenol

Dissolved organic matter (DOM) and dissolved black carbon (DBC) are significant environmental factors that influence the transport of organic pollutants. However, the mechanisms by which their molecular diversity affects pollutant transport remain unclear. This study elucidates the molecular binding sequence and adsorption sites through which DOM/DBC compounds antagonize the transport of 2,4,6-trichlorophenol (TCP) using column experiments and modelling. DBC exhibits a high TCP adsorption rate (kn = 5.32 × 10−22 mol1–n∙Ln–1∙min−1) and conditional stability constant (logK = 5.19–5.74), indicating a strong binding affinity and antagonistic effect on TCP. This is attributed to the high relative content of lipid/protein compounds in DBC (25.65 % and 30.28 %, respectively). Moreover, the small molecule lipid compounds showed stronger TCP adsorption energy (Ead = −0.0071 eV/−0.0093 eV) in DOM/DBC, combined with two-dimensional correlation spectroscopy model found that DOM/DBC antagonized TCP transport in the environment through binding sequences that transformed from lipid/protein small molecule compounds to lignin/tannin compounds. This study used a multifaceted approach to comprehensively assess the impact of DOM/DBC on TCP transport. It reveals that the molecular diversity of DOM/DBC is a critical factor affecting pollutant transport, providing important insights into the environmental trend and ecological effects of pollutants.

Effect of nitrogen-doped activated carbon on formaldehyde adsorption behaviour in different scale pores

The pore size range of activated carbon has an important effect on formaldehyde adsorption, while nitrogen-doped can promote formaldehyde adsorption, but the mechanism of nitrogen-doped on formaldehyde adsorption at different pore size range has not been elaborated clearly. Therefore, this paper investigates the effect of range on formaldehyde adsorption at different pore size scales. Through simulation, it is concluded that nitrogen-doped does not broaden the optimal pore size for formaldehyde adsorption and the optimal pore size is still 6 Å, but nitrogen-doped can improve the non-bonding interactions between formaldehyde molecules and activated carbon by changing the electrostatic distribution on the surface of activated carbon, which enhances the adsorption of formaldehyde molecules. In addition, the non-bonding interaction between formaldehyde molecules and activated carbon decreases with increasing pore size, whereas nitrogen-doped enhances the non-bonding interaction between formaldehyde molecules and activated carbon, and therefore nitrogen-doped improves the limiting pore size of activated carbon for formaldehyde adsorption.

CO2‐Mediated Hydrogen Energy Release‐Storage Enabled by Arc‐Discharge‐Synthesized High‐Dispersion Platinum Catalysts

AbstractDeveloping and fabricating a heterogeneous material for efficient dehydrogenation of formic acid (FA) to H2 coupled with hydrogenation of CO2 back to FA is a promising strategy to forming a carbon‐neutral CO2‐mediated hydrogen energy release‐storage system, which remains challenging. Herein, a facile one‐step ultrahigh‐temperature method of arc‐discharge route for synthesizing efficient single‐crystal α‐MoC supported platinum catalysts with high dispersion of Pt single atoms (SAs), nanoclusters (NCs), and nanoparticles (NPs) is reported. These catalysts exhibit remarkable performance for the adsorption properties and chemical conversion of small molecules including room‐temperature FA dehydrogenation, CO2 hydrogenation to FA (formate), and low‐temperature CO oxidation reactions. The enhanced electron transfer from MoC to active Pt species improves catalyst's surface electron density, thus modulating the chemical adsorption of these small molecules. The engineered 0.1Pt/MoC with Pt SAs shows an outstanding FA dehydrogenation efficiency, with ca. 100% FA conversion and an initial TOF of up to 7739 h−1 at 25 °C. The versatile 0.1Pt/MoC also displays the ability for converting CO2 hydrogenation back to the hydrogen storage carrier FA (formate) with 88.3% yield under mild conditions. Moreover, in‐depth insights into the material microstructure, Pt−MoC electronic interactions, reaction‐dependent particle size effect, and adsorption energy are comprehensively investigated.

Study on the hydrate growth characteristics and rheology of silica-containing sand water-in-oil emulsion system

Understanding the transportability of silica-sand-containing hydrate slurries is crucial for production safety of non-consolidated natural gas hydrate reservoirs, especially when solid-state fluidization technology is utilized. Despite some research on silica sand and marine sediments’ influence on hydrate formation kinetics, rheological studies are scarce for systems with silica sands. The formation process of cyclopentane hydrates under the coexistence of hydrophilic silica particles and surfactants were observed. The effects of the concentration and particle size of silica sands as well as the water cut and surfactant concentration of emulsion on the rheological properties of hydrate slurries were investigated using a rheometer. The results indicated: (1) Hydrophilic sand aggregates were entrapped in water droplets, indirectly affecting the oil–water contact area due to the increase in water droplet volume, which was conducive to the combination of alkanes and water molecules to form a hydrate shell; silica particles provided nucleation sites at the oil–water interface to promote the adsorption and aggregation of cyclopentane molecules. (2) The synergistic effect of silica sand and surfactants significantly shortened the induction time of hydrates and increased the viscosity of the slurry. As the concentration of silica sand (1 wt%, 5 wt%, 10 wt%) increased, the induction time of hydrate formation decreased by 44.8 min. Within the concentration range below 5 wt%, the viscosity of the slurry increased as the concentration increased, with an amplitude of 13830.7 mPa·s. The induction time of hydrate formation decreased with increasing silica sand particle size (2 μm, 6.5 μm, 12 μm), but the size of silica sand particles had no significant effect on the viscosity of the slurry. (3) Hydrate slurries in all systems exhibited shear-thinning behavior. There was no obvious relationship between the yield stress of slurry under different silica sand concentrations. However, the yield stress of the slurry was inversely proportional to the size of silica sand particles. The yield stress decreased by 141.13 Pa when the size of silica sand particles increased from 2 μm to 12 μm. Overall, this study highlighted the influence of silica sand presence on flow safety assurance in solid-state fluidization technology.

Rhodamine B functionalized Titanium dioxide and Silver sulfide adorned Bismuth Ferrite Oxide as a Turn-Off fluorescent sensing probe to organochlorine pesticides

Rhodamine B(RhB) functionalized Bismuth Ferrite Oxide(BFO)/Titanium dioxide(TiO2)/Silver disulfide(AgS)nanoparticles were used to build a fluorescent turn-off sensor for the detection of Chlorpyrifos(CLP). The fluorescence was drastically quenched by the RhB fluorescence resonance energy transfer to the surface of BFO/TiO2/AgS NCs via electrostatic interactions. Then the addition of CLP to RhB@BFO/TiO2/AgSNCs initiates the loss of fluorescence by the adsorption of CLP molecules to the turn-off sensor probe. Under favorable conditions, the linearity between the fluorescence quenching and the concentrations was monitored and the limit of detection was estimated to be 0.006 ppm, 0.004 ppm for 2:1 and 3:1 ratio, with the fluorescence quenching efficiency ranges from 92.9 to 94 %.

Recovery of High-Purity SF6 from Humid SF6/N2 Mixture within a Co(II)-Pyrazolate Framework.

Sulfur hexafluoride (SF6) is extensively employed in the power industry. However, its emissions significantly contribute to the greenhouse effect. The direct recovery of high purity SF6 from industrial waste gases would benefit its sustainable use, yet this represents a considerable challenge. Herein, we report the enrichment of SF6 from SF6/N2 mixtures via adsorptive separation in a stable Co(II)-pyrazolate MOF BUT-53 (BUT: Beijing University of Technology), which features dynamic molecular traps. BUT-53 exhibits an excellent SF6 adsorption uptake of 2.82 mmol/g at 0.1 bar and 298 K, as well as an unprecedented SF6/N2 (10:90) selectivity of 2485. Besides, the remarkable SF6/N2 selectivity of BUT-53 enables recovery of high purity (>99.9%) SF6 from a low concentration (10%) mixture through a breakthrough experiment. The excellent SF6/N2 separation efficiency was also well maintained under humid conditions (RH = 90%) over multiple cycles. Molecular simulation, single-crystal diffraction, and adsorption kinetics studies elucidate the associated adsorption mechanism and water tolerance.

Regulating Catalytic Oxidation Enantiomers Behavior by Imparting Chiral Microenvironment in Zr-Based Metal-Organic Frameworks.

Chiral inversions of enantiomers have significantly different biological activities, so it is important to develop simple and effective methods to efficiently identify optically pure compounds. Inspired by enzyme catalysis, the construction of chiral microenvironments resembling enzyme pockets in the pore space structure of metal-organic frameworks (MOFs) to achieve asymmetric enantioselective recognition and catalysis has become a new research hotspot. Here, a super-stable porphyrin-containing material PCN-224 is constructed by solvothermal method and a chiral microenvironment around the existing catalytic site of the material is created by post-synthesis modifications of the histidine (His) enantiomers. Experimental and theoretical calculations results show that the modulation of chiral ligands around Zr oxide clusters produces different spatial site resistances, which can greatly affect the adsorption and catalytic level of the enantiomeric molecules of tryptophan guests, resulting in a good enantioselective property of the material. It provides new ideas and possibilities for future chiral recognition and asymmetric catalysis.

Chemoselective Adsorption of Allyl Ethers on Si(001): How the Interaction between Two Functional Groups Controls the Reactivity and Final Products of a Surface Reaction.

Selective adsorption of multifunctional molecules is rarely observed when the different functional groups react via nonactivated reaction channels. Although the latter is also the case for ether cleavage and the adsorption of C=C double bonds on the highly reactive Si(001) surface, we find that allyl ethers, which combine both functional groups, react on Si(001) selectively via the cleavage of the molecules' ether group. In addition, our XPS measurements at 90, 150, and 300 K indicate an increased reactivity of the ether group when compared to monofunctional ethers. STM investigations furthermore reveal different final adsorption configurations after ether cleavage of allyl methyl ether when compared to diethyl ether as the monofunctional reference molecule. The interaction of the two functional groups in one molecule thus leads to new reaction channels with higher reactivity for ether cleavage on Si(001). As a further consequence, the reactivity of the C=C double bond is suppressed up to room temperature, leading to the observed selective adsorption.

Transition Metal Chelation Effect in MOF-253 Materials: Guest Molecule Adsorption Dynamics and Proposed Formic Acid Synthesis Investigated by Atomistic Simulations.

The dynamic characterization of guest molecules in the metal-organic frameworks (MOFs) can always provide the insightful and inspiring information to facilitate the synthetic design of MOF materials from the bottom-up design of perspective. Herein, we present a series of atomistic molecular dynamics simulation for investigating the bipyridine dicarboxylate (bpydc) linker rotation effect on guest molecule adsorption with and without considering the transition metal (TM) chelation in MOF-253 materials. The simulated PXRD patterns of the various linker orientations present the challenge of distinguishing these structural varieties by the conventional crystalline spectroscopic measurements. The observed short inter-TM stable structure may subsequently lead to the formation of a binuclear TM catalytic site, and a proposed formic acid generation mechanism from CO2 and H2 is derived based upon the density functional theory calculations for the application of CO2 reduction.