Adsorption Trends Research Articles

Adsorption study of CO and O2 on Au5-x-yAgxCuy [x, y = 1, 3] trimetallic nanoclusters

In present study, we focus on adsorption of CO and O2 gases over different trimetallic nanocluster. Among all trimetallic nanoclusters, copper occupied four coordinated sites and found to be nearly planer. The adsorption of carbon monoxide (CO) at these four coordinated sites drastically changes the structure of all the trimetallic nanoclusters. The adsorption trend of CO followed by all trimetallic nanoclusters is copper, gold and silver respectively. The anomalous behaviour arises due to the relativistic effect in the case of gold. The relativistic effect destabilizes the d-orbital and s-orbital. The destabilized d-orbital enhances the pi-back bonding. Unlike CO, the O2 adsorption at four coordinated Cu-sites does not bring as drastic changes in the geometry of the nanocluster as it in the case of CO adsorption at 4-coordinated Cu-site. In contrast, CO adsorbs on these nanoclusters as one atom on top of another (μ1η1-atop mode), whereas O2 exhibits three types of bonding-bridging mode, atop mode (-μ2η2 or μ2η1 - bridging mode or μ1η1-atop mode).

Application of Date Palm Tree Branch-Based Activated Carbon for Aqueous Toxicity Reduction

The Kingdom of Saudi Arabia (KSA) has millions of date palm trees for commercial scale date-fruit production. The respective industry also generates agricultural waste including date palm tree branches. This rich bio-resource can be used for several beneficial applications. The present study therefore investigated the application of granular activated carbon (GAC) produced using date palm tree branches to successfully remove phenol, p-cresol, and copper from synthetic wastewater. The respective adsorption equilibrium results fitted well to the Langmuir-type adsorption isotherm. Furthermore, the pH-dependent adsorption results both for phenol and p-cresol appeared to follow an anionic-type adsorption behavior (i.e., decreasing adsorption with an increase in aqueous phase equilibrium pH). However, the pH-dependent adsorption finding for copper showed a cationic-type adsorption behavior. These adsorption trends were explained employing the pH-dependent speciation of the respective pollutants. In general, findings from the present work indicate that a high-specific-surface-area (SSABET) GAC material from the date palm tree branches can be successfully employed for aqueous phase pollution control.

Electrochemical Selective Removal of Oxyanions in a Ferrocene-Doped Metal-Organic Framework.

Metal-organic frameworks (MOF) are a class of crystalline, porous materials possessing well-defined channels that have widespread applications across the sustainable landscape. Analogous to zeolites, these materials are well-suited for adsorption processes targeting environmental contaminants. Herein, a zirconium MOF, UiO-66, was functionalized with ferrocene for the selective removal of oxyanion contaminants, specifically NO3-, SO42-, and PO43-. Electrochemical oxidation of the embedded ferrocene pendants induces preferential adsorption of these oxyanions, even in the presence of Cl- in a 10-fold excess. Anion selectivity strongly favoring PO43- (Soxy/comp = 3.80) was observed following an adsorption trend of PO43- > SO42- > NO3- > (10-fold)Cl- in multi-ion solution mixtures. The underlying mechanisms responsible for ion selectivity were elucidated by performing ex situ X-ray photoelectron spectroscopy (XPS) on the heterogeneous electrode surface postadsorption and by calculating the electronic structure of various adsorption configurations. It was eventually shown that oxyanion selectivity stemmed from strong ion association with a positively charged pore interior due to the spatial distribution of charge by oxygen constituents. While ferrocenium provided the impetus for ion migration-diffusion, it was the formation of stable complexes with zirconium nodes that ultimately contributed to selective adsorption of oxyanions.

Differentiated adsorption of acetaminophen and diclofenac via alkyl chain-modified quaternized SBA-15: Insights from molecular simulation

The increasing presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems pose significant environmental concerns. This study addresses this issue by synthesizing quaternized mesoporous SBA-15 (QSBA) with varied alkyl chain lengths of C1QSBA, C8QSBA, and C18QSBA. QSBA utilizes dual mechanisms: hydrophobic interactions via the alkyl chain and electrostatic attraction/ion exchange via the ammonium group. Diclofenac (DCF) and acetaminophen (ACT) were selected as target PPCPs due to their contrasting dissociation properties and hydrophobicity, which are the main characteristics of PPCPs. The adsorption of DCF and ACT revealed that longer alkyl chains enhanced the adsorption capacity of ACT through hydrophobic interactions, whereas dissociated DCF (DCF–) adsorption was superior owing to its high hydrophobicity (log Kow = 4.5) and electrostatic attraction. pH levels between 6 and 8 resulted in a high affinity for DCF–. Notably, among the three alkyl chains, only C18QSBA exhibited the most effective adsorption for DCF–. These PPCPs adsorption trends were confirmed through molecular simulations of adsorption under conditions in which competing ions coexisted. The molecular simulations show that while DCF– has lower adsorption energy than Cl−, OH−, and H3O+ ions in QSBA, enhancing its adsorption under various pH conditions. Conversely, ACT exhibits a higher adsorption energy, which reduces its adsorption efficiency. This suggests the potential application of QSBA with long alkyl chains in the treatment of highly hydrophobic and negatively charged PPCPs. Furthermore, this study emphasizes the importance of simulating adsorption under competing ion conditions.

Ultrasonic assisted removal of methyl orange and bovine serum albumin from wastewater using modified activated carbons: RSM optimization and reusability

Abstract The removal of industrial pollutants from water remains a significant challenge in water treatment processes. This study investigated the efficacy of powder-activated carbon (PAC), thermally modified PAC (TPAC), and chemically modified PAC (CPAC) for removing bovine serum albumin (BSA) and methyl orange (MO) from simulated wastewater. After undergoing treatment, the BET surface area of TPAC increased to 823 m2/g, while that of CPAC increased to 657 m2/g compared to the initial surface area of pristine PAC, which was 619 m2/g. Batch adsorption experiments assisted by ultrasonication were conducted to evaluate the impact of solution pH, initial concentration, and contact time on the adsorption capacities (qmax) of BSA and MO. TPAC demonstrated superior performance, achieving qmax values of 152 mg/g for MO and 133 mg/g for BSA, compared to PAC, which provided qmax values of 124 mg/g and 112 mg/g for BSA, respectively. Furthermore, pH levels of 3 and 5 were identified as highly effective for the removal of MO and BSA from water, respectively. The adsorption kinetics of both MO and BSA followed pseudo2nd-order (R2 > 0.99) reaction kinetics under both batch and ultrasonic conditions, confirming the removal of contaminants through chemisorption. The adsorption trends also satisfied the Langmuir isothermal model, indicating the formation of a uniform monolayer during the adsorption process of these contaminants. To understand the simultaneous effect of all the variables, response surface methodology (RSM) using central composite design (CCD) was used to predict the adsorption capacities of CPAC. After five adsorption cycles, the removal efficiencies of MO (from 98% to 80%) and BSA (from 55% to 40%) decreased in the CPAC system. The results suggested that CPAC can be effectively utilized to remove MO from wastewater.

Adsorption of Polycyclic Aromatic Hydrocarbons from Wastewater Using Iron Oxide Nanomaterials Recovered from Acid Mine Water: A Review

Polycyclic aromatic hydrocarbons (PAHs) are a group of organic pollutants known for their persistence and potential carcinogenicity. Effective removal techniques are required since their presence in wastewater poses serious threats to human health and the environment. In this review study, iron oxide nanomaterials (IONs), a by-product of mining operations, recovered from acid mine water are used to investigate the adsorption of PAHs from wastewater. The mechanisms of PAH adsorption onto IONs are investigated, with a focus on the effects of concentration, temperature, and pH on adsorption efficiency. The better performance, affordability, and reusable nature of IONs are demonstrated by comparative studies with alternative adsorbents such as activated carbon. Economic and environmental ramifications highlight the benefits of employing recovered materials, while case studies and real-world applications show how effective IONs are in removing PAHs in the real world. This review concludes by discussing potential future developments in synthesis processes, areas for more research, and emerging trends in nanomaterial-based adsorption. This research intends to contribute to the development of more effective and sustainable wastewater treatment technologies by offering a thorough assessment of the present and future potential of employing IONs for PAH removal from wastewater.

Operando X-Ray Scattering for Electrocatalysis and Beyond

The energy transition stands as one of the greatest challenges of today’s society. In this context, electrocatalyst materials at the heart of electrochemical energy conversion devices such as fuel cells and water electrolyzers are expected to play an increasing crucial role in the near future. The urgent bottleneck to be overcome in electrocatalyst materials development to allow the widespread deployment of electrochemical systems is thus reaching combined high activity and long-term stability at low cost. Despite the diversity in electrocatalyst materials, the latter being largely imposed by the various types of electrochemical systems (noble vs. non-noble metals in acidic vs. alkaline media for example) and the prerequisites of the different electrochemical processes (oxidation or reduction reactions of various species at different electrode potential ranges), most activity and stability properties of electrocatalysts directly derive from their (surface) chemistry and structure [1]. Such properties (and their temporal evolution) can thus be directly investigated by means of in situ or operando high energy X-ray scattering (XRD) technique [2].In this presentation, the versatility of in situ and operando XRD technique in addressing key bottlenecks in electrocatalyst materials development, notably by probing adsorption and oxidation trends [3], will be showcased. After an overview of previous contributions from the literature, the talk will focus on our ongoing works which encompass the study of Pt-based nanocatalysts for the oxygen reduction reaction (ORR) at proton-exchange membrane fuel cells (PEMFCs) anode, carbon-capped Ni@C catalyst for the hydrogen oxidation reaction (HOR) at anion-exchange membrane fuel cells (AEMFCs) anode and IrCu unsupported aerogel catalyst for the oxygen evolution reaction (OER) at proton-exchange membrane water electrolyzers (PEMWEs) anode.Finally, the ability of operando XRD to provide device-relevant insights at the macroscale (such as ionomer hydration in PEMFCs or water distribution in AEMFCs) beyond electrocatalysts microstructural properties will be presented.

Recovery of rare earth elements from mining wastewater with aminomethylphosphonic acid functionalized 3D-printed filters

Herein we report the use of nylon-12-based 3D-printed filters incorporating α-aminomethylphosphonic acid as an active additive for the recovery of Y, Nd, and Dy from the mining waste solution containing Al, K, Ca, Sc, Fe, Co, Cu, Zn, Y, Nd, Dy, and U. Nylon-12 was chosen for the polymer matrix of the filter due to its inactivity towards the studied metals. The micrometer-level structure of the filters was studied with a scanning helium ion microscope and X-ray tomography to reveal the porosity, pore size, and active additive distribution in the filters. Furthermore, FTIR spectroscopy was used to analyze the compositional changes in the 3D-printed filters after the printing and adsorption processes. Adsorption of the metals was studied at a pH range of 1–4, and the following adsorption trend Sc > Fe > U > Y, Nd, Dy > Al, Cu, Zn > K, Ca, Co was observed in each of the studied pH values. The sequential recovery process for metals was studied at pH 2, and desorption of the metals from the filters was performed with 6 M HNO3. 100 % adsorption of REEs, Fe, and U was achieved during the recovery process, and on average, over 88 % of the adsorbed Y, Nd, and Dy were desorbed from the filters. In contrast to Y, Nd, and Dy, the desorption of Sc, Fe, and U was minimal (Fe and U) or negligible (Sc) with 6 M HNO3 due to their strong coordination to the active additive. Maximum adsorption capacities for Y, Nd, Dy, and U were determined by using linear Langmuir adsorption isotherm. The best maximum adsorption capacity was determined for Sc, Qmax = 0.51 mmol/g followed by U, Nd, Dy, and Y with capacities of 0.47, 0.24, 0.23, and 0.17 mmol/g, respectively. Overall, this study achieved a complete removal of Sc, Fe, and U from the simulated mining waste solution leaving a final eluate that mainly contained Y (320 μg), Nd (350 μg), Dy (330 μg), and Al (710 μg) demonstrating the applicability of the 3D-printed filters in the recovery of Y, Nd, and Dy from the multimetal solution.

Unifying mixed gas adsorption in molecular sieve membranes and MOFs using machine learning

Recent machine learning models to accurately obtain gas adsorption isotherms focus on polymers or metal–organic frameworks (MOFs) separately. The difficulty in creating a unified model that can predict the adsorption trends inside both types of adsorbents is challenging, owing to the diversity in their chemical structures. Moreover, models trained only on single gas adsorption data are incapable of predicting adsorption isotherms for binary gas mixtures. In this work, we address these problems using feature vectors comprising only the physical properties of the gas mixtures and adsorbents. Our model is trained on adsorption isotherms of both single and binary mixed gases inside carbon molecular sieving membrane (CMSM), together with data available from CoRE MOF database. The trained models are capable of accurately predicting the adsorption trends in both classes of materials, for both pure and binary components. ML architecture designed for one class of material, is not suitable for predicting the other class, even after proper training, signifying that the model must be trained jointly for proper predictions and transferability. The model is used to predict with good accuracy the CO2 uptake inside CALF-20 framework. This work opens up a new avenue for predicting complex adsorption processes for gas mixtures in a wide range of materials.

Removal of PFAS by hydrotalcite: Adsorption mechanisms, effect of adsorbent aging, and thermal regeneration

Layered double hydroxides (LDH) have been shown to be effective adsorbents, but their utility for the treatment of per- and polyfluoroalkyl substances (PFAS) in water has not been fully explored. In this study, the adsorption of 9 PFAS on hydrotalcite (HT), a type of LDH, was investigated using reaction solutions with environmentally relevant PFAS concentrations. The adsorption of individual PFAS by HT depended upon a range of factors, including the temperature used to pre-treat (i.e., calcine) the HT, aging conditions, and the presence of anions in the solution. HT calcined near 400 °C most effectively adsorbed PFAS, but its ability to adsorb PFAS was sensitive to storage conditions. The adsorption of CO2 and moisture from air, which likely resulted in the re-intercalation of CO32− into the interlayer regions of HT, was observed to reduce PFAS adsorption and may explain performance loss over time. The adsorption trend among 9 PFAS and the influence on this process by Cl−, NO3−, SO42−, and CO32− indicated that adsorption occurred via a combination of ion exchange, electrostatic attraction, and hydrophobic interactions, although the relative importance of each mechanism deserves further investigation. During this study, we also demonstrated for the first time that HT can be thermally regenerated at 400 °C without affecting its ability to adsorb PFOS and PFBA. Overall, our results suggest that HT may serve as an effective alternative for PFAS treatment.

Removal of Heavy Metal Ions(Fe2+, Mn2+, Cu2+ and Zn2+) on to Activated Carbon Prepared from Kashmiri Walnut Shell (Juglans regia)

Heavy metal pollution poses significant threats to the environment and human health, even at trace concentrations. In this study, activated carbon derived from Kashmiri walnut shell (Juglans regia) was investigated for its potential to adsorb heavy metal ions (Fe2+, Mn2+, Cu2+, and Zn2+). Standard solutions containing heavy metal ions at concentrations ranging from 10 to 50 ppm were prepared for adsorption experiments, i.e., at temperature 25 °C, and adsorbent dosage 1 g using a column mechanism. The activated carbon was first treated with 0.1M HCl and 0.5M ammonia solutions, and then washed with demineralised water. Subsequently, the metal ion solutions were passed through the column individually, and the filtrates were analyzed for heavy metal ion presence. The experimental results demonstrated that walnut shell-derived activated carbon exhibited promising adsorption capacity spanning from 0.36 mg/g for Zn2+, 0.5 mg/g for both Mn2+ and Cu2+ and 0.54 mg/g for Fe2+ thus showing the adsorption trend as Fe2+ > Mn2+ = Cu2+ > Zn2+. This study highlights the potential of using walnut shell-derived activated carbon as an effective and cost-efficient method for mitigating heavy metal pollution in contaminated water sources.

Plasmid size determines adsorption to clay and breakthrough in a saturated sand column

Horizontal gene transfer (HGT) is a major factor in the spread of antibiotic resistant genes (ARG). Transformation, one mode of HGT, involves the acquisition and expression of extracellular DNA (eDNA). eDNA in soils is degraded rapidly by extracellular nucleases. However, if bound to a clay particle, eDNA can persist for long periods of time without losing its transformation ability. To better understand the mechanism of eDNA persistence in soil, this experiment assessed the effects of 1) clay mineralogy, 2) mixed salt solution, 3) plasmid size on DNA adsorption to clay and 4) breakthrough behavior of three differently sized plasmids in an environmentally relevant solution. Batch test methods were used to determine adsorption trends of three differently sized DNA plasmids, pUC19, pBR322, and pTYB21, to several pure clay minerals, goethite (α-FeOOH), illite, and kaolinite, and one environmental soil sample. Results show not all sorbents have equal adsorption capacity based on surface area with adsorption capacities decreasing from goethite > illite = kaolinite > bulk soil, and low ionic strength solutions will likely not significantly alter sorption trends. Additionally, plasmid DNA size (i.e., length) was shown to be a significant predictor of adsorption efficiency and that size affects DNA breakthrough, with breakthroughs occurring later with larger plasmids. Given that DNA persistence is linked to its adsorption to soil constituents and breakthrough, eDNA size is likely an important contributor to the spread of ARG within natural microbial communities.

Exploring porous sulfur copolymers for efficient removal of heavy metal ions from wastewater: A computational study

This study aims to evaluate the efficacy of porous sulfur copolymers (PSSD and NaSD) in adsorbing heavy metals from wastewater through an inverse vulcanization process. A computational fluid dynamics (CFD) model is developed and validated with experimental data to analyze the heavy metal removal by these materials. The results indicate that Arsenic ions exhibit the highest adsorption capacity compared to cadmium, mercury, and lead, indicating a stronger affinity of porous materials for arsenic ions. Lead ions show lower adsorption due to their larger ionic radius and lower charge density in PSSD. The CFD modeling assesses the adsorption process based on material position, revealing that in PSSD, maximum adsorption occurs at 1.5 cm thickness, while in NaSD, lead inhibits adsorption around 1 cm, with other metals continuing slow adsorption until 2 cm. The results also indicate that two parameter isothermal models indicate that the Langmuir model best fits the adsorption data and three isothermal models stipulate that the sips model is suitable for adsorption data. In the case of PSSD, the maximum adsorption trend is; Arsenic (289 µg/g) > cadmium (228 µg/g) > mercury (207 µg/g) > lead (188 µg/g) ions, respectively. The adsorption efficiency of adsorbents is 60–85 % for heavy metal ions removal. This study holds promise for industrial applications due to the availability of bulk sulfur for porous copolymer production. Leveraging CFD simulations enables rapid determination of optimal process parameters tailored to individual chemical plants, thereby enhancing operational efficiency. This groundbreaking approach enables accurate prediction of adsorption data for various heavy metals under consistent conditions, revolutionizing industrial applications.

Time-Resolved Killing of Individual Bacterial Cells by a Polycationic Antimicrobial Polymer.

Polycationic polymers are widely studied antiseptics, and their efficacy is usually quantified by the solution concentration required to kill a fraction of a population of cells (e.g., by Minimum Bactericidal Concentration (MBC)). Here we describe how the response to a polycationic antimicrobial varies greatly among members of even a monoclonal population of bacteria bathed in a single common antimicrobial concentration. We use fluorescence microscopy to measure the adsorption of a labeled cationic polymer, polydiallyldimethylammmonium chloride (PDADMAC, Mw ≈ 4 × 105 g mol-1) and the time course of cell response via a cell permeability indicator for each member of an ensemble of either Escherichia coli, Staphylococcus aureus, or Pseudomonas aeruginosa cells. This is a departure from traditional methods of evaluating synthetic antimicrobials, which typically measure the overall response of a collection of cells at a particular time and therefore do not assess the diversity within a population. Cells typically die after they reach a threshold adsorption of PDADMAC, but not always. There is a substantial time lag of about 5-10 min between adsorption and death, and the time to die of an individual cell is well correlated with the rate of adsorption. The amount adsorbed and the time-to-die differ among species but follow a trend of more adsorption on more negatively charged species, as expected for a cationic polymer. The study of individual cells via time-lapse microscopy reveals additional details that are lost when measuring ensemble properties at a particular time.

Investigating the influence of solvent type and pH on protein adsorption onto silica surface by evanescent-wave cavity ring-down spectroscopy.

Several studies have explored the adsorption of various proteins onto solid-liquid interfaces, revealing the crucial role of buffer solutions in biological processes. However, a comprehensive evaluation of the buffer's influence on protein absorption onto fused silica is still lacking. This study employs evanescent-wave cavity ring-down spectroscopy (EW-CRDS) to assess the influence of buffer solutions and pH on the adsorption kinetics of three globular proteins: hemoglobin (Hb), myoglobin (Mb), and cytochrome c (Cyt-C) onto fused silica. The EW-CRDS tool, with a ring-down time of and a minimum detectable absorbance of , enabled precise optical measurements at solid-liquid interfaces. The three heme proteins' adsorption behavior was investigated at pH 7 in three different solvents: deionized (DI) water, tris(hydroxymethyl)-aminomethane hydrochloride (Tris-HCl), and phosphate buffered saline (PBS). For each protein, the surface coverage, the adsorption and desorption constants, and the surface equilibrium constant were optically measured by our EW-CRDS tool. Depending on the nature of each solvent, the proteins showed a completely different adsorption trend on the silica surface. The adsorption of Mb on the silica surface was depressed in the presence of both Tris-HCl and PBS buffers compared with unbuffered (DI water) solutions. In contrast, Cyt-C adsorption appears to be relatively unaffected by the choice of buffer, as it involves strong electrostatic interactions with the surface. Notably, Hb exhibits an opposite trend, with enhanced protein adsorption in the presence of Tris-HCl and PBS buffer. The pH investigations demonstrated that the electrostatic interactions between the proteins and the surface had a major influence on protein adsorption on the silica surface, with adsorption being greatest when the pH values were around the protein's isoelectric point. This study demonstrated the ability of the highly sensitive EW-CRDS tool to study the adsorption events of the evanescent-field-confined protein species in real-time at low surface coverages with fast resolution, making it a valuable tool for studying biomolecule kinetics at solid-liquid interfaces.

Unraveling the molecular mechanism for enhanced gas adsorption in mixed-metal MOFs via solid-state NMR spectroscopy

The incorporation of multiple metal ions in metal-organic frameworks (MOFs) through one-pot synthesis can induce unique properties originating from specific atomic-scale spatial apportionment, but the extraction of this crucial information poses challenges. Herein, nondestructive solid-state NMR spectroscopy was used to discern the atomic-scale metal apportionment in a series of bulk Mg1-xCox-MOF-74 samples via identification and quantification of eight distinct arrangements of Mg/Co ions labeled with a 13C-carboxylate, relative to Co content. Due to the structural characteristics of metal-oxygen chains, the number of metal permutations is infinite for Mg1-xCox-MOF-74, making the resolution of atomic-scale metal apportionment particularly challenging. The results were then employed in density functional theory calculations to unravel the molecular mechanism underlying the macroscopic adsorption properties of several industrially significant gases. It is found that the incorporation of weak adsorption sites (Mg2+ for CO and Co2+ for CO2 adsorption) into the MOF structure counterintuitively boosts the gas adsorption energy on strong sites (Co2+ for CO and Mg2+ for CO2 adsorption). Such effect is significant even for Co2+ remote from Mg2+ in the metal-oxygen chain, resulting in a greater enhancement of CO adsorption across a broad composition range, while the enhancement of CO2 adsorption is restricted to Mg2+ with adjacent Co2+. Dynamic breakthrough measurements unambiguously verified the trend in gas adsorption as a function of metal composition. This research thus illuminates the interplay between atomic-scale structures and macroscopic gas adsorption properties in mixed-metal MOFs and derived materials, paving the way for developing superior functional materials.

Universal electronic descriptors for optimizing hydrogen evolution in transition metal-doped MXenes

The integration of transition metal (TM) atoms into two-dimensional (2D) transition metal carbides and nitrides (MXenes) has been identified as a promising strategy for enhancing hydrogen evolution reaction (HER) performance. However, the vast combinatorial space presents challenges for rapid catalyst screening. In response, high-throughput calculations were conducted on Ti2CO2 and Zr2CO2 doped with a wide array of TM single atoms. The local structural and corresponding electronic structural changes were analyzed, with an emphasis on their implications for HER performance. Furthermore, universal electronic descriptors were developed using the Sure Independence Screening and Sparsifying Operator (SISSO) method, harmonizing the Gibbs free energy of hydrogen adsorption (ΔGH*) trends across different MXenes substrates doped with TM atoms. These descriptors enabled the prediction of Cr, Fe, Ru, Pd, Os, and Ir as effective dopants for optimizing the ΔGH* of Hf2CO2, resulting in a reduction of ΔGH* from 1.082 eV to within ±0.2 eV. Our work not only highlights the potential of these TM dopants in significantly enhancing the catalytic activity of MXenes but also underscores the value of universal electronic structure descriptors in rapidly identifying and developing high-performance HER catalysts.

A detailed molecular dynamics simulation and experimental investigation of CO2 adsorption on graphene oxide-polyaniline nanocomposite

The study investigated the sorption and diffusion of carbon dioxide on Graphene oxide-polyaniline (GO-PANI) using volumetric method and molecular dynamics simulations. The experimental results showed that GO-PANI was more effective at adsorbing CO2 than either of the individual materials alone. Simulations supported this trend in CO2 adsorption and provided additional insights into the structural information of the adsorbents and the dynamics of CO2 molecules. The Langmuir adsorption model was employed to fit sorption isotherms computed using Grand Canonical Monte Carlo (GCMC) method. The GO-PANI nanocomposite compound exhibited a superior adsorption rate compared to pure structures. The isosteric heat for CO2 adsorption was 27.59 kJ/mol. The interaction energy of single molecules of CO2 on GO-PANI surface was −38.075 kcal/mol. Diffusion coefficient value for CO2 was 41.2 × 10 −9 m2/s, lower than that of the pure polymer. FT-IR, FE-SEM, and BET techniques were used to analyze synthesized GO-PANI structure. The highest CO2 adsorption was observed at a temperature of 283 K. Isosteric heat adsorption decreased with uniform surface charge. This research provides critical microscopic information on gas adsorption in polymer nanocomposites and demonstrates the effectiveness of GO-PANI as an efficient adsorbent for carbon dioxide, which could be useful in various industrial applications.

Biopolymer-metal composites for selective removal and recovery of waterborne orthophosphate

Orthophosphate (Pi) remediation from effluent serves to address global water security by preventing eutrophication. Herein, chitosan (C), alginate (Alg) and three respective metal systems (Fe3+, Al3+, Cu2+) were used to prepare binary (BMC) or ternary (TMC) metal composite adsorbents. Their physicochemical properties were analyzed through XPS, IR and TGA, while the adsorption properties of the composites were characterized via adsorption isotherms and single-point experiments in saline environmental water. Al-composites formed Al–O complexes, while Fe- and Cu-composites formed in the presence of the biopolymer backbone FeO(OH) and Cu2(OH)3NO3, respectively. While Al-composites showed the highest bound water fraction (up to 16%), the Cu-composites (Cu-TMC-N, CuC-BMC-N; where N = nitrate) revealed the lowest water content. Alginate-based binary composites showed slightly higher water content, as compared to ternary and binary chitosan composites. Among the four materials (Al-TMC-N, Fe-TMC-N, Cu-TMC-N and CuC-BMC-N), the Al-TMC showed the highest Pi selectivity over sulfate, along with high Pi removal-% even in a binary mixture (sulfate + orthophosphate) despite the presence of competitive anion species. Upon spiking saline groundwater samples with low Pi (5 mg/L) that contains 2060 or 6030 mg/g sulfate, Al-TMC-N showed the highest Pi selectivity, followed by Fe-TMC-N. This trend in adsorption of Pi among the various composites is understood based on the HSAB principle for the conditions employed in this study. Removal efficiencies of Pi above 60% in Well 1 (ca. 2000 mg/L sulfate) and above 30% in Well 3 (ca. 6030 mg/L sulfate). Herein, environmentally compatible and sustainable composite adsorbents were prepared that reveal selective Pi recovery from (highly) saline groundwater that can mitigate eutrophication in aqueous media.

Geo-storage of hydrogen in organic-rich shales: Multicomponent selectivity of organic nanopores

The gas adsorption capacity of kerogen is commonly obtained through experimental isothermal adsorption procedures. These experiments employ mathematical models called adsorption isotherms, which bridge the gap between empirical data and theoretical frameworks to offer a continuous representation of the underlying processes in the depleted shale formation with some fraction of resident adsorbed natural gas. However, an exploration of the adsorption behavior of H2, in the presence of CH4, C2H6, C3H8, and CO2 in organic-rich porous media of varying pore size remains an unaddressed area of study. Considering this, in this study, we conduct a molecular simulation of the adsorption and diffusion behavior of hydrogen (H2), methane (CH4), ethane (C2H6), propane (C3H8), and carbon dioxide (CO2) within a representative kerogen organic nanopore structure. In particular, we studied hydrogen adsorption behavior in organic-rich shale formations in varying nanopore size and multi-gas components. We also evaluate the suitability of different adsorption models (Langmuir, Langmuir-Freundlich, Toth) for depicting the adsorption characteristics of single species. For the multicomponent mixture (H2/CO2/CH4/C2H6/C3H8), we apply Langmuir ratio correlation model (LRC). The findings indicate C3H8 demonstrates the highest adsorption potential, while CH4 ranks lowest, followed by H2, CO2 and C2H6 exhibit intermediate potential. Furthermore, the adsorption of each species is hindered by organic nanopores of 1 nm, as opposed to 2 nm nanopores. For multicomponent adsorption, hydrogen exhibits minimal presence at equilibrium, which can be attributed to its higher diffusivity compared to other gases. Notably, the Langmuir, Toth, and Langmuir-Freundlich models exhibit ability to accurately depict the overall adsorption trends single-component. However, for the multicomponent mixture (H2/CO2/CH4/C2H6/C3H8), the LRC is found reasonable effective to capture the adsorption.