A novel approach for the modification of eggshell powder and its application for lead and methylene blue removal.

Water pollution is one of the major concerns due to rapid industrialization and urbanization. Wastewater treatment has been an area of great interest for the researchers and among many technologies developed for water treatment, adsorption is the most preferred due to its efficiency and ability of been economical method. In this research, eggshell powder (ESP) is converted into modified eggshell powder (MESP) through chemical and thermal treatment (at 550 °C for 2 h) to use it as an adsorbent to remediate Pb2+ and Methylene blue (MB) from water, then it is transferred into modified eggshell powder magnetic composite (MESPMC) with iron coating to resolve the separation challenges and to boost the MESP's adsorption efficiency. FTIR analysis identified the functional groups of ESP, MESP, and MESPMC. XRD analysis reveals a hexagonal crystal structure of calcite in MESP and a combination of the hexagonal crystal structure of calcite and the cubic crystal structure of iron in MESPMC. The Scherrer equation is used to determine the average crystallite sizes of MESP and MESPMC, which are 22.59 nm and 12.15 nm, respectively. The SEM image shows the irregular shape of the MESP and MESPMC particles, as well as the active coating layer in MESPMC. EDX analysis reveals that Ca (20.92 %), O (56.83 %), and Fe (41.03 %), O (48.83 %) are the most abundant elements in MESP and MESPMC respectively. TGA analysis points out that MESPMC outperforms MESP in terms of thermal stability between 600 and 750 °C. MESP and MESPMC were found to be very efficient adsorbent for lead and methylene blue in aqueous medium. At 40 mg/mL adsorbent dosage, ESP, MESP, and MESPMC had the highest yields of Pb2+ removal, with 46.996 %, 99.27 %, and 99.78 % respectively at 200 rpm for 60 min with 25 °C. Furthermore, at the 0.5 mg/mL adsorbent dosage, ESP, MESP, and MESPMC have the maximum removal efficiency of methylene blue, with 47.19 %, 90.1 %, and 92 %, respectively at 200 rpm for 30 min with 25 °C. In both cases, the removal efficiency of MESPMC is slightly higher than that of MESP and much higher than that of ESP. Additionally, the results confirm that MESP and MESPMC are potential environment-friendly bio sources to remediate heavy metal (Pb2+) and methylene blue dye from water.

Understanding the effect of adsorption sites of CO at cobalt surface on its reactivity with H2/H by DFT calculations.

Cobalt (Co) is widely used in Fischer-Tropsch synthesis (FTS), converting synthesis gas, carbon monoxide + hydrogen (CO + H2), to long-chain hydrocarbons. The adsorption of CO on the Co surface is the key step in FTS. In this work, the effect of CO adsorption sites on the reactions between CO and H2 was investigated by using density functional theory (DFT). The energetics and structures of the reactions between the adsorbed CO (CO*) and H2/adsorbed H2 (H2*)/adsorbed H atom (H*) were calculated. The results show that the reaction between CO* and H2 is initiated by the molecular adsorption of H2 on the Co surface. The reactions between CO* and H2*/H* are influenced by CO adsorption sites. For the reaction system of CO* + H2*, it has the lowest reaction barrier when CO is adsorbed at the hcp site, while for CO* + H*, it has the lowest reaction barrier when CO is adsorbed on the top site. Kinetic analysis indicates that to improve the reactivity of CO + H2 in FTS, the adsorption of CO should be controlled to favour the top and bridge sites. This article is part of the theme issue 'Celebrating the 15th anniversary of the Royal Society Newton International Fellowship'.

Digging Its Own Site: Linear Coordination Stabilizes a Pt1/Fe2O3 Single-Atom Catalyst.

Determining the local coordination of the active site is a prerequisite for the reliable modeling of single-atom catalysts (SACs). Obtaining such information is difficult on powder-based systems and much emphasis is placed on density functional theory computations based on idealized low-index surfaces of the support. In this work, we investigate how Pt atoms bind to the (11̅02) facet of α-Fe2O3; a common support material in SACs. Using a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and an extensive computational evolutionary search, we find that Pt atoms significantly reconfigure the support lattice to facilitate a pseudolinear coordination to surface oxygen atoms. Despite breaking three surface Fe-O bonds, this geometry is favored by 0.84 eV over the best configuration involving an unperturbed support. We suggest that the linear O-Pt-O configuration is common in reactive Pt-based SAC systems because it balances thermal stability with the ability to adsorb reactants from the gas phase. Moreover, we conclude that extensive structural searches are necessary to determine realistic active site geometries in single-atom catalysis.

Competitive Adsorptive Mechanism of H2/N2 in LTA/FAU Zeolites by Molecular Simulations and Experiments.

For industrial tail gas to be converted into high-purity hydrogen, the H2-N2 mixture needs to be separated efficiently. This work examined the adsorption characteristics and competitive mechanisms of H2 and N2 on LTA- and FAU-type zeolites, at 77 K, 298 K, and 0.1-10 bar by thoroughly analyzing results of adsorption capacity experiments and molecular simulations. In the Grand Canonical Monte Carlo (GCMC) simulations, the force field causing a molecular dipole of H2 and the polarization force field of N2 are first applied. The accuracy of the force field was experimentally verified. The findings indicate that N2 and H2 loading on Ca-FAU (Ca-LTA) are higher than Na-FAU (Na-LTA). On NaX at 77 K, the highest adsorption selectivity (N2/H2) is observed; on NaA at 298 K, it is the opposite. The GCMC data findings demonstrate that H2 and N2 have remarkably similar adsorption sites, with framework oxygen atoms and non-framework cations serving as the main adsorption sites for adsorbate molecules. Furthermore, the rate at which H2 diffuses is higher than that of N2. The study of redistribution charge before and after adsorption demonstrated that N2 has a greater affinity for the framework oxygen atoms than H2. This study provides a molecular theoretical foundation for the adsorption behavior of H2-N2 mixture in zeolites.

Regulating Water Adsorption Sites of Keto-Enamine COF by Base Exfoliation and Deprotonation for Enhanced Humidity Response.

Covalent organic framework (COF) has received much attention owing to its unique framework structure formed by diverse organic units. However, challenges, including low conductivity, structure instability, and limited control of adsorption and desorption processes, stimulate the modification of COF in electronic sensors. Herein, inspired by the alterable structure of COF in different solvents, a facile base exfoliation and deprotonation method is proposed to regulate the water adsorption sites and improve the intrinsic conductivity of TpPa-1 COF. TpPa-1 COF powders are exfoliated to nanosheets to increase water adsorption, while the deprotonation is utilized to adjust the affinity of water molecules on TpPa-1 COF framework, contributing to water accumulation in the 1D pores. The as-fabricated TpPa-1 COF sensor exhibits a decreased recovery time from 419 to 49 s, forming a linear relation between relative humidity (RH) value and humidity response. The excellent chemical stability of the covalent bond of TpPa-1 COF contributes to the excellent stable device performance in 30 days, promoting further integration and data analysis in respiration monitoring.

Study on the mechanism of lignin non-productive adsorption on cellobiohydrolase.

Enzymatic hydrolysis is important for lignocellulosic biomass conversion into fermentable sugars. However, the nonproductive adsorption of enzyme on lignin was major hinderance for the enzymatic hydrolysis efficiency. In this study, non-productive adsorption mechanism of cellulase component cellobiohydrolase (CBH) onto lignin was specific investigated. Research revealed that the adsorption behavior of CBH on eucalyptus alkali lignin (EuA) was affected by reaction conditions. As study on the adsorption kinetic, it was indicated that the adsorption cellulose binding domain (CBD) of CBH onto EuA well fitted with Langmuir adsorption model and pseudo second-order adsorption kinetics model. And the tyrosine site related to the adsorption of CBD onto lignin was proved by the fluorescence and UV spectra analysis. The results of this work provide a theoretical guidance to understanding the nonproductive adsorption mechanism and building method to reduce the adsorption of cellulase on the lignin.

Unique Hierarchically Structured High-Entropy Alloys with Multiple Adsorption Sites for Rechargeable Li-CO2 Batteries with High Capacity.

Lithium-carbon dioxide (Li-CO2) batteries offer the possibility of synchronous implementation of carbon neutrality and the development of advanced energy storage devices. The exploration of low-cost and efficient cathode catalysts is key to the improvement of Li-CO2 batteries. Herein, high-entropy alloys (HEAs)@C hierarchical nanosheet is synthesized from the simulation of the recycling solution of waste batteries to construct a cathode for the first time. Owing to the excellent electrical conductivity of the carbon material, the unique high-entropy effect of the HEAs, and the large number of catalytically active sites exposed by the hierarchical structure, the FeCoNiMnCuAl@C-based battery exhibits a superior discharge capability of 27664 mAh g-1 and outstanding durability of 134 cycles as well as low overpotential with 1.05 V at a discharge/recharge rate of 100 mA g-1. The adsorption capacity of different sites on the HEAs is deeply understood through density functional theory calculations combined with experiments. This work opens up the application of HEAs in Li-CO2 batteries catalytic cathodes and provides unique insights into the study of adsorption active sites in HEAs.

Study of CHF3/CH2F2 Adsorption Separation in TIFSIX-2-Cu-i.

Hydrofluorocarbons (HFCs) have important applications in different industries; however, they are environmentally unfriendly due to their high global warming potential (GWP). Hence, reclamation of used hydrofluorocarbons via energy-efficient adsorption-based separation will greatly contribute to reducing their impact on the environment. In particular, the separation of azeotropic refrigerants remains challenging, such as typical mixtures of CH2F2 (HFC-23) and CHF3 (HFC-32), due to a lack of adsorptive mechanisms. Metal-organic frameworks (MOFs) can provide a promising solution for the separation of CHF3-CH2F2 mixtures. In this study, the adsorption mechanism of CHF3-CH2F2 mixtures in TIFSIX-2-Cu-i was revealed at the microscopic level by combining static pure-component adsorption experiments, molecular simulations, and density-functional theory (DFT) calculations. The adsorption separation selectivity of CH2F2/CHF3 in TIFSIX-2-Cu-i is 3.17 at 3 bar under 308 K. The existence of similar TiF62- binding sites for CH2F2 or CHF3 was revealed in TIFSIX-2-Cu-i. Interactions between the fluorine atom of the framework and the hydrogen atom of the guest molecule were found to be responsible for determining the high adsorption separation selectivity of CH2F2/CHF3. This exploration is important for the design of highly selective adsorbents for the separation of azeotropic refrigerants.

Radiation Resistance and Adsorption Behavior of Aluminum Hexacyanoferrate for Pd.

Irradiation resistance is important for adsorbents used in radioactive environments such as high-level liquid waste. In this work, a silica-based composite adsorbent (KAlFe(CN)6/SiO2) was synthesized and γ-irradiated from 10 to 1000 kGy. The angles of the main X-ray diffraction peaks slightly decreased with the increase in irradiation dose, and a minor decomposition of CN- occurred after irradiation to 1000 kGy, indicating that the KAlFe(CN)6/SiO2 adsorbent could preserve structural integrity with a dose below 100 kGy. In 1 to 7 M HNO3, the adsorption ability of the irradiated KAlFe(CN)6/SiO2 remained performant, with a higher Kd than 1625 cm3 g-1. The adsorption equilibrium of Pd(II) in 3 M HNO3 was attained within 45 min before and after irradiation. The maximal adsorption capacity Qe of the irradiated KAlFe(CN)6/SiO2 on Pd(II) ranged from 45.1 to 48.1 mg g-1. A 1.2% relative drop in Qe was observed after 100 kGy irradiation, showing that γ-irradiation lower than 100 kGy insignificantly affected the adsorption capacity of KAlFe(CN)6/SiO2. Calculating and comparing the structures and free energies of different adsorption products via the density functional theory (DFT) method showed that KAlFe(CN)6/SiO2 was more inclined to completely adsorb Pd(II) and spontaneously generate Pd[AlFe(CN)6]2.

Adsorptive decontamination of antibiotics from livestock wastewater by using alkaline-modified biochar.

Efficient abatement of antibiotics from livestock wastewater is in urgent demand, but still challenging. In this study, alkaline-modified biochar with larger surface area (130.520 m2 g-1) and pore volume (0.128 cm3 g-1) was fabricated and explored for the adsorption of different types of antibiotics from livestock wastewater. Batch adsorption experiments demonstrated that the adsorption process was mainly determined by chemisorption and was heterogeneous, which could be moderately affected by the variations of solution pH (3-10). Furthermore, the computational analysis based on density functional theory (DFT) indicated that the -OH groups on biochar surface could serve as the dominant active sites for antibiotics adsorption due to the strongest adsorption energies between antibiotics and -OH groups. In addition, the antibiotics removal was also evaluated in multi-pollutants system, where biochar performed synergistic adsorption towards Zn2+/Cu2+ and antibiotics. Overall, these findings not only deepen our understandings on the adsorption mechanism between biochar and antibiotics, but also promote the application of biochar in the remediation of livestock wastewater.

Hydrophilic Amino Groups Acted in the Hydrophobic Reaction Environment for Efficient Hydrogen Isotopes Enrichment.

Hydrogen isotope enrichment through liquid-phase catalytic exchange (LPCE) technology is achieved in a hydrophobic reaction environment to avoid liquid water poisoning, but the usage of hydrophobic support severely inhibits the internal diffusion of water molecules to decrease the catalytic efficiency. Herein, we encapsulate platinum active sites into a metal organic framework (Pt@NH2-UiO-66) as the efficient catalyst for LPCE via introducing hydrophilic amino groups. Experiments and density functional theory simulation reveal amino groups in the channel as the adsorption site of water molecules accelerates the internal diffusion and slows down the accumulation on the platinum sites. Meanwhile, the amino groups interact with the Pt site bridge electron transfer from active sites to support the host, thus decreasing the catalytic reaction and generated water desorption barrier. Due to these positive roles, the turnover frequency of Pt@NH2-UiO-66 reaches 2272 h-1 in a microchannel reactor. This work provides a novel design strategy of catalysts in LPCE.

In situ scrutinize the adsorption of sulfamethoxazole in water using AFM force spectroscopy: Molecular adhesion force determination and fractionation.

The interaction force of a typical antibiotic molecule during adsorption has never been experimentally determined and fractionated, which hindered the evolution of removal strategies. In this study, sulfamethoxazole (SMX) as a typical antibiotic was stably immobilized onto an atomic force microscopy (AFM) tip without affecting original properties. The SMX modified AFM tip visualized the potential adsorption sites on a graphene oxide (GO) nanosheet for the first time by mapping the SMX adhesion force distribution. Moreover, the interaction force of a single SMX molecule to GO was determined at 38.6 pN which was subsequently fractionated into the hydrophobic (17.9 pN) and π-π (160.0 pN) attractions as well as the electrostatic repulsion (- 139.3 pN) at pH: 5.7. As compared with highly-ordered pyrolytic graphite (HOPG), the introduced oxygen containing groups on GO not only reduced the hydrophobic interaction but also generated an opposite electrostatic repulsion force to SMX. This study experimentally and theoretically revealed the adhesion mechanisms of SMX and potentially other sulfonamide antibiotics in molecular level, which may contribute to the study of antibiotic environmental transportation and the development of next-generation antibiotic remediation protocols.

Adsorption Site Selective Occupation Strategy within a Metal-Organic Framework for Highly Efficient Sieving Acetylene from Carbon Dioxide.

The separation of acetylene and carbon dioxide is an essential but challenging process owing to the similar molecular sizes and physical properties of the two gas molecules. Notably, these molecules usually exhibit different orientations in the pore channel. We report an adsorption site selective occupation strategy by taking advantage of differences in orientation to sieve the C2 H2 from CO2 in a judiciously designed amine-functionalized metal-organic framework, termed CPL-1-NH2 . In this material, the incorporation of amino groups not only occupies the adsorption sites of CO2 molecules and shields the interaction of uncoordinated oxygen atom and CO2 molecules resulting in a negligible adsorption amount and a decrease in enthalpy of adsorption but also strengthened the binding affinity toward C2 H2 molecules. This material thus shows an extremely high amount of C2 H2 at low pressure and a remarkably high C2 H2 /CO2 IAST selectivity (119) at 1 bar and 298 K.

Insights into the Gas Adsorption Mechanisms in Metal-Organic Frameworks from Classical Molecular Simulations.

Classical molecular simulations can provide significant insights into the gas adsorption mechanisms and binding sites in various metal-organic frameworks (MOFs). These simulations involve assessing the interactions between the MOF and an adsorbate molecule by calculating the potential energy of the MOF-adsorbate system using a functional form that generally includes nonbonded interaction terms, such as the repulsion/dispersion and permanent electrostatic energies. Grand canonical Monte Carlo (GCMC) is the most widely used classical method that is carried out to simulate gas adsorption and separation in MOFs and identify the favorable adsorbate binding sites. In this review, we provide an overview of the GCMC methods that are normally utilized to perform these simulations. We also describe how a typical force field is developed for the MOF, which is required to compute the classical potential energy of the system. Furthermore, we highlight some of the common analysis techniques that have been used to determine the locations of the preferential binding sites in these materials. We also review some of the early classical molecular simulation studies that have contributed to our working understanding of the gas adsorption mechanisms in MOFs. Finally, we show that the implementation of classical polarization for simulations in MOFs can be necessary for the accurate modeling of an adsorbate in these materials, particularly those that contain open-metal sites. In general, molecular simulations can provide a great complement to experimental studies by helping to rationalize the favorable MOF-adsorbate interactions and the mechanism of gas adsorption.

Evaluation of the performance of zirconia-multiwalled carbon nanotube nanoheterostructures in adsorbing As(III) from potable water from the perspective of physical chemistry and chemical physics with a special emphasis on approximate site energy distribution.

In this study, the performance of zirconia-multiwalled carbon-nanotube nanoheterostructure in adsorbing the highly toxic water-contaminant As(III) from water has been probed from the perspective of physical chemistry and chemical physics. The adsorbent found extremely efficient in adsorbing As(III) from potable water. Moreover, its ability to oxidize As(III) to As(V) in the aqueous solution has been evinced by the XPS studies. The values of the maximum adsorption capacities (qm) depend on the isotherm studied and in this study, no wonder different values of qm are obtained for different adsorption isotherms. The thermodynamic studies advocate the exothermic and spontaneous nature of the adsorption process. Calculation on density functional theory (DFT) also suggested the exothermic nature of the adsorption process. DFT calculation further revealed the role of the Zr-O and Zr-OH bridges in binding As(III) species on the zirconia surface. However, this study finds an adverse effect of visible light-irradiation on the adsorption process. Furthermore, this study propounds an approach to estimate the maximum solubility of As(III) in water combining the Cerofolini's condensation-approximation and Polanyi adsorption potential. Detailed analysis on the approximate adsorption site energy distribution (f(E*)) further finds an inconsistency in the formula used to estimate qm using f(E*), which underestimates qm. The inconsistency, for the very first time, has successfully been resolved by modifying the heterogeneity related parameter in f(E*).

Improving enzymatic hydrolysis of acid-pretreated bamboo residues using amphiphilic surfactant derived from dehydroabietic acid.

In this work, amphiphilic surfactant was obtained using dehydroabietic acid from pine rosin and then pre-adsorbed with acid-pretreated bamboo residues (AP-BR) to block the residual lignin adsorption site, which is expected to improve its enzymatic digestibility. Results from cryogenic-transmission electron microscopy (Cryo-TEM) indicated amphiphilic surfactant with PEG with polymerization degree of 34 (D-34) aggregated to form worm-like micelles, which improved enzymatic hydrolysis yield of AP-BR from 24.3% to 71.9% by pre-adsorbing with 0.8 g/L. Amphiphilic surfactants pre-adsorbed on AP-BR could reduce hydrophobicity of AP-BR, adsorption affinity and adsorption capacity of lignin for cellulase from 0.51 L/g to 0.48-0.32 L/g, from 2.9 mL/mg to 1.8-1.4 mL/mg, and from 122.3 mg/g to 101.9-21.4 mg/g, respectively. These changed properties showed compelling positive contributions (R2 > 0.9) for free enzymes in the supernatants and sequently for final enzymatic hydrolysis yield, which was caused by blocking non-productively hydrophobic adsorption between lignin and cellulase.

Adsorption site-dependent transport of diclofenac in water saturated minerals and reference soils.

Use of reclaimed water for irrigation is a main way for pharmaceutical compounds such as diclofenac getting into the soil environment. However, the role of minerals, especially iron oxides, in the diclofenac adsorption to soils with low soil organic matter (SOM) is still in the lack of evaluation. In this study, adsorption of diclofenac onto six minerals (five nature minerals-hematite, goethite, magnetite, kaolinite and aluminium oxide and one engineered mineral-activated aluminia) and five reference soils was investigated by column chromatography. Adsorption of diclofenac onto minerals and soils was totally reversible and interactions such as H-bonding were the primary mechanisms. Adsorption affinity of iron oxides was much higher than that of nature silicon and aluminum oxides. Diclofenac tended to be adsorbed by mineral surface -OH groups with high thermodynamic stability, which were dehydroxylated at high temperature. Compared with the SOM-dominated sorption of naphthalene, adsorption of diclofenac onto soils was controlled by bonding with surface -OH groups of iron oxides. Adsorption coefficients of diclofenac onto soils can be well predicted by contents of extracted Fe by diethylenetriamine pentaacetic acid (DTPA) instead of total iron oxides contents, suggesting that the bonding was adsorption site-dependent. These findings highlighted the importance of iron oxides in the adsorption of diclofenac (an anionic pharmaceutical compound) in soils with relatively low SOM (e.g., 1.03-3.45%). It also indicated that contents of effective surface -OH groups and DTPA-Fe were the promising parameters to develop the predictive models for diclofenac adsorption onto minerals and soils, respectively.

Prototypical Organic-Oxide Interface: Intramolecular Resolution of Sexiphenyl on In2O3(111).

The performance of an organic semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. Although an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material are essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In2O3(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide, is based on. The onset of nucleation and formation of the first monolayer are followed with atomically resolved scanning tunneling microscopy and noncontact atomic force microscopy (nc-AFM). Annealing to 200 °C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests an essentially planar adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with a poor long-range order. Eventually, the molecules reorient into an ordered monolayer. This first monolayer has a densely packed, well-ordered (2 × 1) structure with one 6P per In2O3(111) substrate unit cell, that is, a molecular density of 5.64 × 1013 cm-2.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif.

Surface-Enhanced Infrared Spectroscopic Study of a CO-Covered Pt Electrode in Room-Temperature Ionic Liquid.

ATR-SEIRAS is extended for the first time to study potential-induced surface and interface structure variation of a CO-covered Pt electrode in a room-temperature ionic liquid of N-butyl-N-methyl-piperidinium bis((trifluoromethyl)sulfonyl)imide (or [Pip14][TNf2]). Owing to a wide effective potential window of [Pip14][TNf2], a gradual conversion from bridged COad (COB) to terminal COad (COL) is observed in response to positively going potentials, suggesting that [Pip14](+) may be involved in a strong electrostatic interaction with the COad. This site conversion enables the ratio of the apparent absorption coefficient of COL to that of COB to be determined. Also, the spectral results reveal the potential-dependent COad frequency variations as well as the potential-induced interfacial ionic reorientation and movement at the Pt/CO/[Pip14][TNf2] interface.