Adsorption Interaction Research Articles

The addition of fluorine atoms and alkyl chains to aromatic ligand dipole for enhancing stability and photoelectronic properties of formamidinium perovskite surfaces

The long-term stability on perovskite surfaces limits the practical application of perovskite solar cells (PSCs). Adding multifunction ligand can deal with this issue, however, the structure diversity of ligand and perovskite surface leads to the complicated adsorptive interaction, affecting the improvement effect of the stability and photoelectric properties. In this work, strongly electronegative fluorine atoms and alkyl chain with different length are introduced into aromatic ligand dipole to modify the polarity, regulating the phase stability, energy state and photoelectric properties of formamidinium perovskite (FAPbI3) surfaces. The results show the adsorption and interaction energy of positive ligand dipoles on the I-terminated surface decrease with the increase of polarity, which displays stronger ordered π-π stack and adsorption anchoring of ligand dipoles and thus decreasing the formation energy to improve the phase stability. The positive 4-Trifluoromethyl-phenethylammonium (CF3-PEA) with the highest polarity obtains the highest stability and shifts work function (WF) upward from 6.21 eV to the highest 6.46 eV. The negative CF3-PEA adsorbs on the PbI2-terminated surface induced by CF3•••Pb and π•••I interaction, achieving the stable phase with lower formation energy and lowest WF 5.61 eV. This work provides tutorial for optimizing performance of PSCs by the addition of ligand dipoles.

Temperature-Dependent Frictional Behavior of MoS2 in Humid Environments: Insights from Water Molecule Adsorption and DFT Analyses.

This study investigates the temperature-dependent frictional behavior of MoS2 in humid environments within the context of a long-standing debate over increased friction due to oxidation processes or molecular adsorption. By combining sliding friction experiments and density functional theory (DFT)-based first-principles simulations, it aims to clarify the role of water molecule adsorption in influencing frictional properties of MoS2, addressing the challenge of identifying interfacial bonding behavior responsible for friction in such conditions. Sliding experiments revealed that magnetron-sputtered MoS2 exhibits a reduction in the coefficient of friction (COF) with an increase in temperature from 25 to 100 °C under 20 and 40% relative humidity. This change in the COF obeys the Arrhenius law, presenting an energy barrier of 0.165 eV, indicative of the temperature-dependent nature of these frictional changes and suggests a consistent frictional mechanism. DFT simulations showed that H2O molecules are adsorbed at MoS2 vacancy defects with adsorption energies ranging from -0.56 to -0.17 eV, which align with the experimentally determined energy barrier. Adsorptive interactions, particularly the formation of stable H···S interfacial hydrogen bonds at defect sites, increase the interlayer adhesion and impede layer shearing. TEM analysis confirms that although MoS2 layers align parallel to the sliding direction in humid conditions, the COF remains at 0.12, as opposed to approximately 0.02 in dry air. This demonstrates that parallel layer alignment does not notably decrease the COF, underscoring humidity's significant role in MoS2's COF values, a result also supported by the Arrhenius analysis. The reversibility of the physisorption process, demonstrated by the recovery of the COF in high-temperature humid environments, suggests its dynamic nature. This study yields fundamental insights into MoS2 interfaces for environments with variable humidity and temperature, crucial for demanding tribological applications.

Pyrolyzed coal base high surface area and mesoporous activated carbon for methyl violet 2B dye removal: Optimization of preparation conditions and adsorption key parameters

Herein, a low-grade Malaysian coal namely Merit Karpit coal (MRTKC) was transformed into high surface area mesoporous activated carbon (MRTKC-AC) via pyrolysis-assisted ZnCl2 activation. A numerical optimization approach rooted in the Box-Behnken design (BBD) was employed to determine the best operational conditions such as A: dosage of MRTKC-AC (ranging from 0.02 to 0.1 g/100 mL), B: the pH of the solution (varying from 4 to 10), and C: the contact time (ranging from 5 to 25 min). A notable surface area of 1229.1 m2/g and a distinctive mesoporous structure with an average pore diameter of 2.9 nm was achieved at optimum impregnation ratio (1 MRTKC: 2 ZnCl2), heating temperature 500 °C, and residence time 60 min. Moreover, the application of MRTKC-AC was evaluated through the removal of methyl violet (MV) from the aqueous environment. The comprehensive equilibrium and kinetic adsorption analyses showed that the adsorption of MV by MRTKC-AC matched closely to the Langmuir isotherm model, while the kinetic behavior was suitably described by the pseudo-second order model. Thus, the maximum adsorption capacity (qmax) for MV dye onto MRTKC-AC was ascertained to be a substantial 238.6 mg/g. The MV dye adsorption mechanism onto MRTKC-AC surface indicates various dye–adsorbent interactions: electrostatic attraction, p–p interaction, and H-bonding. This work shows that Malaysian low-rank coal is an economical precursor for producing low-cost and efficient mesoporous activated carbon with substantive surface area.

Synthesis of N/P/S Co-doped porous carbons by carbonizing polyphosphazene microspheres for highly selective adsorption of Pb (II)

Heteroatom-doping has emerged as a promising approach for enhancing the properties of carbon materials, particularly in the treatment of heavy-metal wastewater. However, the simultaneous synthesis of multi-heteroatom co-doped carbon materials poses significant complexity and challenges. Consequently, there is an increasing demand for the development of non-toxic and straightforward methods to prepare such materials. In this study, we present a novel approach for the synthesis of N/P/S co-doped porous carbonaceous adsorbents using polyphosphazene as precursors. Our focus is specifically on their effectiveness in adsorbing Pb (II). The results reveal that the synthesized adsorbents, denoted as carbonized polyphosphazene or CZ-600 exhibited a high carbon content co-doped with N, P and S atoms, as well as an abundance of oxygen-containing functional groups and a porous structure. These characteristics collectively contribute to the exceptional adsorption capacity of CZ-600 for Pb (II), with a maximum adsorption capacity of 121.7 mg/g and an equilibrium time as short as 20 min. Further investigations of the adsorption process involve fitting adsorption isotherm, kinetic, and thermodynamic models, revealing chemical adsorption as the predominant mechanism, supported by contributions from micropore adsorption and electrostatic interactions. This work proposes a sustainable and efficient solution for the treatment heavy-metal wastewater, which not only advances the understanding of heteroatom-doped carbon materials but also provides valuable insights into their practical applications in environmental remediation.

Simultaneous removal of NOx and VOCs by Si doping CeO2 based catalysts: An acidity and redox properties balance strategy

The synergetic catalytic removal of nitrogen oxides (NOx) and volatile organic compounds (VOCs) exhibits huge potentials in reducing cost with high efficiency in the field of environmental catalysis, the key point is to adjust the balance of acidity and oxidizability over one catalyst. Herein, we develop a modifited CeO2-based catalyst by doping Si to balance acidity and redox properties. Consequently, the mosted optimizted Si-doped CeO2 catalyst showed superior synergistic removal of NOx and toluene compared to pure CeO2. It was demonstrated that Si-doped CeO2 improved markedly the number of acidic sites, increased the Ce3+ concentration, and adjusted the adsorption interaction between catalyst and NH3/toluene. These led to a wider temperature window of 300–375 °C for the simultaneous removal of NOx and toluene. It is believed that this work provides a simple strategy to balance acidity and redox properties and offers novel insights for multi-pollutant removal catalyst design.

Unravelling the reaction mechanism for H2 production via formic acid decomposition over Pd: Coverage-Dependent microkinetic modeling

As a key liquid organic hydrogen carrier, investigating the decomposition of formic acid (HCOOH) on the Pd (111) transition metal surface is imperative for harnessing hydrogen energy. Despite a multitude of studies, the major mechanisms and key intermediates involved in the dehydrogenation process of formic acid remain a great topic of debate due to ambiguous adsorbate interactions. In this research, we develop an advanced microkinetic model based on first-principles calculations, accounting for adsorbate–adsorbate interactions. Our study unveils a comprehensive mechanism for the Pd (111) surface, highlighting the significance of coverage effects in formic acid dehydrogenation. Our findings unequivocally demonstrate that H coverage on the Pd (111) surface renders formic acid more susceptible to decompose into H2 and CO2 through COOH intermediates. Consistent with experimental results, the selectivity of H2 in the decomposition of formic acid on the Pd (111) surface approaches 100 %. Considering the influence of H coverage, our kinetic analysis aligns perfectly with experimental values at a temperature of 373 K.

Development of a method for analyzing the positional correlation of local structures in scanning probe microscopy images using template-matching image-processing method

The functionalities of materials are governed by the atom type and arrangement, and perturbations caused by defects and adsorbate interactions often significantly alter the behavior of materials. Scanning probe microscopy (SPM) can capture complex interactions caused by the structures on surfaces. It is, however, difficult to analyze such interactions appearing there. In this paper, an image-processing technique that employs template matching to recognize local structures in SPM images and calculate positional correlations is reported. This approach opens new avenues for investigating intricate perturbations in the sciences and provides detailed insights into materials science.

Exploring the mechanisms of diazinon adsorption onto alpha and beta cyclodextrins through molecular dynamics simulations: Insights into environmentally friendly pesticide remediation

This study investigated the adsorption of Diazinon on α and β-Cyclodextrins (CDs) through Molecular Dynamics Simulations. The entrance point variation in diazinon adsorption is analyzed, revealing distinct preferences for entry into α and β-CDs. The center of mass distance of diazinon and CDs is investigated, highlighting the dynamic behavior within β-CD. Interaction energies between diazinon, CD, and water are explored, emphasizing the significance of van der Waals interactions in diazinon adsorption. Hydrogen bonding analysis reveals preferential adsorption of diazinon on α-CD, attributed to the number and arrangement of hydrogen bonds. Free energy calculations using the Bennett acceptance ratio method indicate a stronger affinity of diazinon for α-CD, supported by molecular electrostatic potential maps. The study also examines the hydration capacity and water molecules' distribution, indicating differences between α and β-CD. Radial distribution function analysis (RDF) illustrates the adsorption process, emphasizing water molecule expulsion upon diazinon entry. Structural stability is assessed through root mean squared deviation, indicating equilibrium attainment. Gibbs free energy calculations suggest stronger hydrophobic interactions in the α-CD cavity. This comprehensive analysis contributes valuable insights into the MD of diazinon-CDs interactions, shedding light on their adsorption mechanisms and potential applications in wastewater treatment.

Origins of Selective Oxidation in Carbon-Based Nonradical Oxidation Processes toward Organic Pollutants: Quantitative Structure-Activity Relationships (QSARs).

Metal-free carbon material-mediated nonradical oxidation processes (C-NOPs) have emerged as a research hotspot due to their excellent performance in selectively eliminating organic pollutants in aqueous environments. However, the selective oxidation mechanisms of C-NOPs remain obscure due to the diversity of organic pollutants and nonradical active species. Herein, quantitative structure-activity relationship (QSAR) models were employed to unveil the origins of C-NOP selectivity toward organic pollutants in different oxidant systems. QSAR analysis based on adsorption and oxidation descriptors revealed that C-NOP selectivity depends on the oxidation potentials of organic pollutants rather than on adsorption interactions. However, the dominance of electronic effects in selective oxidation decreases with increasing structural complexity of organic pollutants. Moreover, the oxidation threshold solely depends on the inherent electronic nature of organic pollutants and not on the reactivity of nonradical active species. Notably, the accuracy of substituent descriptors (Hammett constants) and theoretical descriptors (e.g., highest occupied molecular orbital energy, ionization potential, and single-electron oxidation potential) is significantly influenced by the complexity and molecular state of organic pollutants. Overall, the study findings reveal the origins of organic pollutant-oriented selective oxidation and provide insight into the application of descriptors in QSAR analysis.

Semi-automated filter micro-solid phase extraction based on urea-formaldehyde microsphere followed by corona discharge-ion mobility spectrometry for simultaneous detection of fentanyl and nor-fentanyl in urine

In this work, semi-automated filter micro-solid phase extraction (SA-FμSPE) packed by urea–formaldehyde (UF) microspheres coupled with corona discharge ionization-ion mobility spectrometry (CD-IMS) was developed for the extraction and determination of fentanyl and nor-fentanyl in urine samples. UF microspheres, synthesized by aqueous polymerization, can be used to achieve effective extraction of analytes through multiple adsorption interactions such as hydrophobic, dipole–dipole and hydrogen bonding interactions. UF microspheres dispersed in methanol were packed in the filter by syringe, and the extraction process was performed by a portable automatic filter extraction device. The parameters affecting extraction efficiency (i.e., extraction time, the flow rate of extraction, pH value, amount of sorbent, ionic strength, cycle times of desorption, and type of eluent) were investigated. Then, the eluate containing fentanyl and nor-fentanyl was simultaneously analyzed by CD-IMS in positive mode. Under the optimal extraction conditions, the detection limits for the target compounds were 5.00 ng mL−1 and 8.00 ng mL−1, respectively. The spiked recoveries were in the range of 81.97 % −112.37 % by testing the real samples and validated by UHPLC-MS. Thus, the satisfactory results reveal that SA-FμSPE coupled with CD-IMS has great potential for on-site extraction and detection of fentanyl and nor-fentanyl in urine samples.

Microscopic perspective of the combined collector CTAB/SPA on the flotation separation of fluorite and calcite: Adsorption morphology and interaction force

It is difficult to separate fluorite and calcite due to their similar surface properties. This article applied combined collector cetyltrimethylammonium bromide (CTAB)/styrene phosphonic acid (SPA) to separate fluorite from calcite and explored the adsorption morphology and interaction force. Flotation results indicated that effective separation between fluorite and calcite with CTAB/SPA at a molar ratio of 1:1, at the concentration of 1×10−4 mol/L and pH 11.0. Surface tension measurements indicated a synergistic effect of CTAB/SPA in solution. The combined collector increased the hydrophobicity difference between fluorite and calcite surfaces. Zeta potential measurements illustrated that both CTAB and SPA adsorbed on fluorite and calcite surfaces, with CTAB as the main collector. Atomic force microscope (AFM) analysis further demonstrated that more CTAB/SPA adsorbed on fluorite surface than that on the calcite surface, resulting in a stronger hydrophobic force between fluorite particles. It was concluded that CTAB, as the main collector in the combined collector, adsorbed on the fluorite surface, while SPA interspersed between the CTAB molecules, with an adsorption model proposed. These macroscopic and microscopic points provide a possibility for the flotation separation between fluorite and calcite.

TiN as Radical Scavenger in Fe─N─C Aerogel Oxygen Reduction Catalyst for Durable Fuel Cell.

Fe─N─C is the most promising alternative to platinum-based catalysts to lower the cost of proton-exchange-membrane fuel cell (PEMFC). However, the deficient durability of Fe─N─C has hindered their application. Herein, a TiN-doped Fe─N─C (Fe─N─C/TiN) is elaborately synthesized via the sol-gel method for the oxygen-reduction reaction (ORR) in PEMFC. The interpenetrating network composed by Fe─N─C and TiN can simultaneously eliminate the free radical intermediates while maintaining the high ORR activity. As a result, the H2O2 yields of Fe─N─C/TiN are suppressed below 4%, ≈4 times lower than the Fe─N─C, and the half-wave potential only lost 15mV after 30 kilo-cycle accelerated durability test (ADT). In a H2─O2 fuel cell assembled with Fe─N─C/TiN, it presents 980mAcm-2 current density at 0.6V, 880mWcm-2 peak power density, and only 17mV voltage loss at 0.80Acm-2 after 10 kilo-cycle ADT. The experiment and calculation results prove that the TiN has a strong adsorption interaction for the free radical intermediates (such as *OH, *OOH, etc.), and the radicals are scavenged subsequently. The rational integration of Fe single-atom, TiN radical scavenger, and highly porous network adequately utilize the intrinsic advantages of composite structure, enabling a durable and active Pt-metal-free catalyst for PEMFC.

Humic substances mediated superior photochemical pollutant conversion on defective TiO2 in environmentally relevant matrices: The key roles of oxygen vacancy in surface interactions, oxidant activation and radical generation

Ubiquitous humic substances usually exhibit strong interfering effects on target pollutant removal in advanced water purification. This work aims to develop a photochemical conversion system on the nonstoichiometric TiO2 for pollutant removal in environmentally relevant matrices. In this synergistic reaction system, the redox-reactive humic substances and defective oxygen vacancies can serve as the organic electron transfer mediator and the key surface reactive sites, respectively. This system achieves a superior pollutant degradation in real surface water at low oxidant concentrations. Reactive oxygen vacancies on the TiO2 surface and sub-surface are of considerable interest for this photochemical reaction system. By engineering defective oxygen vacancies on high-energy {001} polar facet, the surface and electronic interactions between tailored TiO2 and humic substances are greatly strengthened for the promoted electron transfer and oxidant activation. Rendered by the strong surface affinity and molecular activation, defective oxygen vacancies thermodynamically and dynamically promote reactive chain reactions for free radical formation, including the selective O2 reduction to ·O2− and the H2O2 activation to ·OH. Our findings take new insights into environmental geochemistry, and provide an effective strategy to in-situ boost the humic substances-mediated water purification without secondary pollution. Environmental implicationHumic substances are widely distributed in aquatic environment, thus playing important roles in environmental geochemistry. For example, humic substances can achieve good surface adsorption through electrostatic adsorption, ligand exchange and electronic interactions with typical TiO2 to form reactive ligand-metal charge transfer complexes for pollutant degradation. Inspired by the unique properties of surface and sub-surface oxygen vacancies, the defective TiO2 was designed to refine the humic substances-mediated photochemical reactions. A superior reactivity was measured for pollutant degradation. Our findings provide an effective strategy to boost naturally photochemical decontamination in environmentally relevant matrices.

Adsorption mechanism and interactions of coal particles modified with a novel hyperbranched dispersant

This account, a hyperbranched dispersant (Es-SAF-DBM-PSS) was assembled with the skeleton of Es-SAF-DBM (the functional modification of hydroquinone-based sulfonated acetone formaldehyde (SAF)) and numbers of linear polystyrene sodium sulfonate (PSS) chains by single electron transfer living radical polymerization (SET-LRP) in the system of PhBr2m4/Cu wire/PMDETA. The structure of the synthesized Es-SAF-DBM-PSS was detected by FTIR, 1H NMR, XPS, UV and GPC. Series of tests about the polymerization kinetics of Es-SAF-DBM-PSS were executed. Effects of temperatures and initiator concentration on the apparent polymerization rate were investigated, the results showed the low activation energy and higher initiation rate fitted the characteristic of SET-LRP. The rheological behaviors of Es-SAF-DBM-PSS as dispersant applied to coal water slurry (CWS) were tested. The following results were found as expected: the best usage of Es-SAF-DBM-PSS was only 0.3%, maximum coal content reached 63.7%, the viscosity dropped as low as 1000mPa·s. And the penetration ratio of slurry mixed with Es-SAF-DBM-PSS was still 100% even after 35days. Adsorption mechanism and interparticle interactions of coal particles modified with Es-SAF-DBM-PSS were investigated by Langmuir equation, dynamic equations and extended Derjaguin-Landau-Verwey-Overbeek (eDLVO) theory, the results showed the excellent dispersion and stability performance of Es-SAF-DBM-PSS were mainly related to the specific hyperbranched structure.

Hydrogen Impact: A Review on Diffusibility, Embrittlement Mechanisms, and Characterization.

Hydrogen embrittlement (HE) is a broadly recognized phenomenon in metallic materials. If not well understood and managed, HE may lead to catastrophic environmental failures in vessels containing hydrogen, such as pipelines and storage tanks. HE can affect the mechanical properties of materials such as ductility, toughness, and strength, mainly through the interaction between metal defects and hydrogen. Various phenomena such as hydrogen adsorption, hydrogen diffusion, and hydrogen interactions with intrinsic trapping sites like dislocations, voids, grain boundaries, and oxide/matrix interfaces are involved in this process. It is important to understand HE mechanisms to develop effective hydrogen resistant strategies. Tensile, double cantilever beam, bent beam, and fatigue tests are among the most common techniques employed to study HE. This article reviews hydrogen diffusion behavior, mechanisms, and characterization techniques.

Bridging the Adsorption Data and Adsorption Process by Introducing a Polynomial Structure To Accurately Describe IUPAC Isotherms, Stepwise Isotherms, and Stepwise Breakthrough Curves.

Porous heterogeneous adsorbents, those composed of multiple pore structures and surface chemical adsorption sites, can result in various gas or vapor adsorption isotherms, including five types of IUPAC adsorption isotherms and stepwise adsorption isotherms that have been difficult to model using a single adsorption equilibrium model. The limitation of the above equilibrium model further restricts the calculations of complex stepwise breakthrough curves. To bridge the adsorption data and adsorption process, it is important to first develop a simple model or method to describe these isotherms of various complex adsorption systems. In this work, assuming that the effect of the diffusion rate can be neglected under the static condition and the adsorption process is discontinuous, the number of adsorption isotherm inflection points can be used to represent the changed number of adsorption interactions. With the introduction of the polynomial structure, a series of empirical or semi-empirical polynomial adsorption models were developed. The N-site polynomial Langmuir-Freundlich equation could accurately fit common type I, II, III, IV, and V adsorption isotherms and complex stepwise adsorption isotherms covering various adsorbates, such as volatile organic compounds (VOCs), toxic industrial chemicals (TICs), water vapor, and carbon dioxide, as well as different adsorbents, such as metal/covalent organic frameworks (MOFs/COFs), zeolites, and porous carbons. Similarly, the introduction of a polynomial structure, such as the N-site polynomial Yoon-Nelson equation, was also successful in the description of interesting stepwise breakthrough curves. This work provides a more accurate adsorption equilibrium model to characterize all types of isotherms. As a foundation model, it is expected to be used to simulate the gas-solid adsorption process inside the fixed and fluidized beds packed with porous adsorbents.

Reinforcement learning for in silico determination of adsorbate-substrate structures.

Reinforcement learning (RL) methods have helped to define the state of the art in the field of modern artificial intelligence, mostly after the breakthrough involving AlphaGo and the discovery of novel algorithms. In this work, we present a RL method, based on Q-learning, for the structural determination of adsorbate@substrate models in silico, where the minimization of the energy landscape resulting from adsorbate interactions with a substrate is made by actions on states (translations and rotations) chosen from an agent's policy. The proposed RL method is implemented in an early version of the reinforcement learning software for materials design and discovery (RLMaterial), developed in Python3.x. RLMaterial interfaces with deMon2k, DFTB+, ORCA, and Quantum Espresso codes to compute the adsorbate@substrate energies. The RL method was applied for the structural determination of (i) the amino acid glycine and (ii) 2-amino-acetaldehyde, both interacting with a boron nitride (BN) monolayer, (iii) host-guest interactions between phenylboronic acid and β-cyclodextrin and (iv) ammonia on naphthalene. Density functional tight binding calculations were used to build the complex search surfaces with a reasonably low computational cost for systems (i)-(iii) and DFT for system (iv). Artificial neural network and gradient boosting regression techniques were employed to approximate the Q-matrix or Q-table for better decision making (policy) on next actions. Finally, we have developed a transfer-learning protocol within the RL framework that allows learning from one chemical system and transferring the experience to another, as well as from different DFT or DFTB levels.

Standardization and micromechanistic study of tetracycline adsorption by biochar

Modification serves as an excellent approach to enhancing the adsorption performance of biochar for tetracycline. Selective modification further allows the attainment of biochar materials that are not only more efficient but also cost-effective. However, the key structural factors influencing the adsorption of tetracycline by biochar remain unclear at present, hindering the effective guidance for modification strategies. This study established the relationship between carbonization degree and adsorption capacity, constructed a standardized microscopic model for biochar adsorption of tetracycline, and explored potential reaction mechanisms. The results indicated that with increases in the degree of carbonization, the tetracycline adsorption capacity of biochar increased from 16.08 mg L−1 to 98.35 mg L−1. The adsorption energy exhibited a strong correlation with the aromatic condensation of biochar at p ≤ 0.01, with a linear relationship (r2 ≥ 0.94). For low carbonization degrees, the adsorption of tetracycline by biochar was primarily driven by chemical bonds (69.21%) and complemented with electrostatic interactions, weak van der Waals forces or π-π interactions. For high carbonization degrees, the synergistic effects of hydrogen bonding, van der Waals forces, and π-π interactions determined the adsorption of tetracycline on biochar (91.1%). Additionally, larger carbon clusters resulted in stronger and more stable adsorption interactions. Furthermore, carboxyl-functionalized highly carbonized biochar displayed the highest reaction energy of − 1.8370 eV for adsorption of tetracycline through electrostatic interactions. This study suggests that a high degree of aromatic condensation in the carbon structure of biochar is crucial for the efficient adsorption of tetracycline.Graphical

Density functional theory study of B‐ and Si‐doped carbons and their adsorption interactions with sulfur compounds

AbstractUnderstanding the adsorption interactions between carbon materials and sulfur compounds has far‐reaching impacts, in addition to their well‐known important role in energy storage and conversion, such as lithium‐ion batteries. In this paper, properties of intrinsic B or Si single‐atom doped, and B–Si codoped graphene (GR) and graphdiyne (GDY) were investigated by using density functional theory‐based calculations, in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds. Results showed that both B or Si single‐atom doping and B–Si codoping could substantially enhance the electron transport properties of GR and GDY, improving their surface activity. Notably, B and Si atoms displayed synergistic effects for the codoped configurations, where B–Si codoped GR/GDY exhibited much better performance in the adsorption of sulfur‐containing chemicals than single‐atom doped systems. In addition, results demonstrated that, after B–Si codoping, the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR, indicating that B–Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Water-based Synthesis of MIL-53(Al) at Room Temperature: An Eff ective Adsorbent for Oxytetracycline (OTC) Antibiotic Removal from Water

MIL-53(Al), a fl exible metal-organic framework, was synthesized by a facile method through a water-based method at room temperature, aligning with the principles of green chemistry. The objective was to investigate its effectiveness in removing pharmaceuticals and personal care products (PPCPs), specifi cally focusing on oxytetracycline (OTC). Our fi ndings revealed that MIL-53(Al) possesses a structure with both micropores and mesopores, with a specifi c surface area of 916 m2/g. MIL-53(Al) notably exhibited a higher OTC adsorption capacity than commercially available powder activated carbon (PAC). The adsorption kinetics followed a pseudo-second-order model, while the Langmuir model accurately described the experimental isotherms for OTC adsorption. MIL-53(Al) outperformed previously reported MOF-based adsorbents with a maximum of 1005 mg/g capacity at pH 7. The fl exible structure induces a breathing effect that signifi cantly improves intraparticle diffusion for OTC, contributing to its adsorption effi ciency. The adsorption of OTC was infl uenced by the solution pH, the acid dissociation constants of OTC, and the charged surface of the adsorbent. Pore fi lling, hydrogen bonding, π-π interaction, electrostatic interaction, and hydrophobic interaction were all associated with the adsorptive interaction between OTC and MIL-53(Al). The MIL-53(Al) also demonstrated good regeneration and reuse, with just a little decreased adsorption capacity after three reuse cycles. These fi ndings indicate that green material MIL-53(Al) has the potential to be an effective adsorbent for removing OTC from water matrices