Adsorption Of Species Research Articles

Preparation of high oxygen vacancies catalyst CeO2/Al2O3-SiC and its mechanism in enhancing the catalytic ozonation of organic pollutants in coal chemical wastewater

The complete harmless treatment of aromatic organic compounds in coal chemical wastewater (CCW) has always been a big challenge in water process engineering. This study addresses the issue by designing and preparing a kind of Ce and Al bimetallic catalyst with high oxygen vacancies (OVs) based on SiC carrier. The results showed that CeO2 and Al2O3 were uniformly dispersed on SiC, and the composite material exhibited an ordered cubic structure. The degradation efficiency and enhancement mechanism of the catalyst with ozone oxidation were investigated. When applied to actual CCW with a chemical oxygen demand (COD) concentration exceeding 600 mg/L, the synergy between O3 and CeO2/Al2O3-SiC increased the degradation efficiency of phenols from 50 % to 99 % and COD from 42 % to 78 % compared to using O3 alone. CeO2/Al2O3-SiC had a high concentration of oxygen vacancies (OVs = 48.57 %). Further research indicated that oxygen vacancies (OVs) were the main active sites for ozone adsorption and reactive oxygen species (ROSs) generation. Electron paramagnetic resonance (EPR) and quenching experiments also confirmed that O3, •O2−1, 1O2 were the main active oxidation factors, rather than •OH. Additionally, even after granulating the catalyst, it still achieved 99 % degradation of phenols. Therefore, this study provides theoretical support for the complete harmless treatment of CCW and has broad prospects for industrial application.

Isolating Cu-Zn active-sites in Ordered Intermetallics to Enhance Nitrite-to-Ammonia Electroreduction

Electrocatalytic nitrite reduction to the valuable ammonia is a green and sustainable alternative to the conventional Haber-Bosch method for ammonia synthesis, while the activity and selectivity for ammonia production remains poor at low nitrite concentrations. Herein, we report a nanoporous intermetallic single-atom alloy CuZn (np/ISAA-CuZn) catalyst with completely isolated Cu-Zn active-sites, which achieves neutral nitrite reduction reaction with a remarkable NH3 Faradaic efficiency over 95% and the highest energy efficiency of ≈ 59.1% in wide potential range from −0.2 to −0.8 V vs. RHE. The np/ISAA-CuZn electrocatalyst was able to operate stably at 500 mA cm−2 for 220 h under membrane electrode assembly conditions with a stabilized NH3 Faraday efficiency of ~80% and high NO2‒ removal rate of ~100%. A series of in situ experimental studies combined with density functional theory calculations reveal that strong electronic interactions of isolated Cu-Zn active-sites altered the protonation adsorption species, effectively alleviating the protonation barrier of *NO2 and thus greatly facilitating the selective reduction of NO2− into NH3.

Understanding the Roles and Regulation Methods of Key Adsorption Species on Ni-Based Catalysts for Efficient Hydrogen Oxidation Reactions in Alkaline Media.

This review focuses on recent advancements in the development and understanding of nickel-based catalysts for the hydrogen oxidation reaction in alkaline media. Given the economic and environmental limitations associated with platinum group metals, nickel-based catalysts have emerged as promising alternatives due to their abundance, lower cost, and comparable catalytic properties. The review begins with an exploration of the fundamental HOR mechanisms, emphasizing the key roles of the reactive species in optimizing the catalytic activity of Ni-based catalysts. Thermodynamic and stability optimizations of nickel-based catalysts are thoroughly examined, focusing on alloying strategies, heteroatom incorporation, and the use of various support materials to enhance their catalytic performance and durability. The review also addresses the challenge of catalyst poisoning, particularly by carbon monoxide, and evaluates the effectiveness of different approaches to improve poison resistance. Finally, the review concludes by summarizing the key findings and proposing future research directions to further enhance the efficiency and stability of nickel-based catalysts for practical applications in anion exchange membrane fuel cells. The insights gained from this comprehensive analysis aim to contribute to the development of cost-effective and sustainable catalysts and facilitate the broader adoption of AEMFCs in the quest for clean energy solutions.

Enhanced Removal Performance and Economical Efficiency of Volatile Organic Sulfur Compounds by Silver-Modified ZSM-5 Zeolites under a High-Humidity Environment: A Mechanistic Study of the Adsorption-Plasma Catalytic Process.

Dimethyl sulfide (DMS) is a harmful volatile organic sulfur compound (VOSC), which must be effectively controlled. The adsorption-plasma catalytic (APC) process is an efficient and economical route for the elimination of low-concentration VOSCs; however, there are still many challenges in humid environment. In this study, a series of zeolites with different Si/Al ratios and Ag loadings were designed, and were performed for DMS removal by APC process. At 80% relative humidity, the DMS adsorption capacity of Ag5-ZSM25 reached 33.9 mg/g, which was 7.9 times that of ZSM25 and nearly 2 times that of Ag5-ZSM200. Analyses via UV-vis, X-ray photoelectron spectroscopy (XPS), and CO-FTIR confirmed that Ag+ was the predominant species for DMS adsorption and degradation in Ag5-ZSM25. DMS-temperature-programmed desorption (TPD) and density functional theory (DFT) calculations indicated that Ag+ significantly enhanced the binding energy with DMS and weakened the competitive adsorption impact of H2O. In the plasma regeneration stage, Ag5-ZSM25 demonstrated an 89% mineralization, with Ag+ being crucial for DMS mineralization. Based on the in situ plasma DRIFT spectra, a possible degradation pathway for DMS was proposed. The APC process achieved an energy efficiency of 1.66 g/kWh, tripling that of the continuous plasma catalytic process and providing guidance for low-concentration DMS elimination.

Computational modeling of petroleum purification for removal of sulfur compounds: Process analysis for reduction of environmental impacts and material costs

In the course of this investigation, three machine learning models (Gaussian Process Regression, Decision Tree Regression, and Kernel Ridge Regression) were examined for determining the correlation between the input variables (x and y) which are spatial coordinates of model’s geometry, and the content of species in adsorption for sulfur capture. For the process modeling, mass transfer was analyzed, and the concentration distribution of sulfur compound was obtained via numerical solution of mass transfer equations, and then used for machine learning models. The machine learning models were trained using a dataset of 19,000 observations, and their performance was assessed through metrics including R2 score, MAE, and RMSE. Analysis of the results reveals that Decision Tree Regression surpassed the other two models in performance, with an R2 score of 0.9989, MAE of 6.64405E-01, and RMSE of 1.1277E+00. Gaussian Process Regression had an R2 score of 0.97106, MAE of 3.65541E+00, and RMSE of 5.6821E+00, while Kernel Ridge Regression had an R2 score of 0.86347, MAE of 8.26121E+00, and RMSE of 1.1330E+01. The Clonal Selection Algorithm was used for hyper-parameter optimization for all models. These findings demonstrate the potential of machine learning techniques for accurately and reliably predicting the concentration of chemical species and highlight the importance of considering the choice of model and hyper-parameter optimization for optimal performance.

Novel S-scheme derived Mo–Bi2WO6/WO3/Biochar composite for photocatalytic removal of Methylene Blue dye

Presently, the distinct charge transport and interface interaction of the S-scheme heterojunction has garnered significant interest. Herein, a S-scheme-based charge transportation Mo-doped Bi2WO6/WO3/Biochar heterojunction was synthesized in situ using a coprecipitation technique to improve methylene blue adsorption and photocatalytic reactive oxygen species production. The doped Mo altered the band gap of Bi2WO6 to increase light absorption, which can facilitate electron-hole separation and transfer. Likewise, the S-scheme band structure improved sunlight utilization, enhanced the reduction and oxidation power of photogenerated electrons, and boosted charge carrier separation and transfer. Thus, due to the synergetic impact of doping and the S scheme band structure, the photocatalysts efficiently eliminated Methylene blue up to 87.5 % in 30 min of photoirradiation. Fabricated heterojunction Mo–Bi2WO6/WO3/Biochar photocatalyst have highest Kapp values 0.02816 min−1 while Mo–Bi2WO6/WO3, Mo–Bi2WO6, Bi2WO6, and WO3 photocatalysts have 0.02816, 0.02273, 0.01527, 0.00643, and 0.00735 min−1, respectively which was 4.38 times greater than pristine Bi2WO6. The study offers a novel perspective for the in-situ production of S-scheme heterojunction with doping to remove different types of contaminants.

Biodegradation of organic micropollutants by anoxic denitrification: Roles of extracellular polymeric substance adsorption, enzyme catalysis, and reactive oxygen species oxidation

The control of organic micropollutants (OMPs) in water environments have received significant attention. Denitrification was reported to exhibit good efficiency to remove OMPs, and the mechanisms involved in are too intricate to be well illustrated. In this study, we selected nitrobenzene [NB] and bisphenol A [BPA] as model pollutants and aimed to unravel the mechanisms of Paracoccus Denitrificans in the removal of OMPs, with a specific emphasis on aerobic behavior during denitrification processes. We demonstrated the formation of extracellular superoxide radicals, i.e., extracellular •O2-, using a chemiluminescence probe and found that extracellular polymeric substance adsorption, extracellular •O2-, and microbial assimilation contributed approximately 40 %, 10 %, and 50 % to OMPs removal, respectively. Transcriptome analysis further revealed the high expression and enrichment of several pathways, such as drug metabolism-other enzymes, of which a typical aerobic enzyme of polyphenol oxidase [PPO] participates in the degradation of NB and BPA. Importantly, all the immediate products showed a significant decrease in toxicity during the aerobic activity-related OMPs degradation process based on the proposed degradation pathways. This study demonstrates the formation of extracellular •O2- and the mechanisms of extracellular •O2-- and PPO-mediated OMPs biodegradation, and offers new insights into OMPs control in widely-used denitrification treatment processes.

Selective Electrooxidation of Crude Glycerol to Lactic Acid Coupled With Hydrogen Production at Industrially-Relevant Current Density.

Transforming glycerol (GLY, biodiesel by-product) into lactic acid (LA, biodegradable polymer monomer) through sustainable electrocatalysis presents an effective strategy to reduce biodiesel production costs and consequently enhance its applications. However, current research faces a trade-off between achieving industrially-relevant current density (>300mA cm-2) and high LA selectivity (>80%), limiting technological advancement. Herein, a Au3Ag1 alloy electrocatalyst is developed that demonstrates exceptional LA selectivity (85%) under high current density (>400mA cm-2). The current density can further reach 1022mA cm-2 at 1.2V versus RHE, superior to most previous reports for GLY electrooxidation. It is revealed that the Au3Ag1 alloy can enhance GLY adsorption and reactive oxygen species (OH*) generation, thereby significantly boosting activity. As a proof of concept, a homemade flow electrolyzer is constructed, achieving remarkable LA productivity of 68.9mmolh-1 at the anode, coupled with efficient H2 production of 3.5 Lh-1 at the cathode. To further unveil the practical possibilities of this technology, crude GLY extracted from peanut oil into LA is successfully transformed, while simultaneously producing H2 at the cathode. This work showcases a sustainable method for converting biodiesel waste into high-value products and hydrogen fuel, promoting the broader application of biodiesel.

Fe reaction sites enhance the removal of tetracycline over Fe-Bi3O4Br with intensified adsorption and photocatalysis

An adsorption-coupling photocatalytic degradation system is a promising strategy for removing emerging pollutants with coexisting substances. Here, Fe-Bi3O4Br was designed and prepared via a hydrothermal method, which intensified tetracycline adsorption and reactive oxygen species formation originated from molecular oxygen. The improvements in adsorption and photocatalytic activity enhanced the generation and utilization of active species, leading to an increase of over 30 % in removal efficiency of tetracycline. Adsorption experiments proved that Fe doping optimized the specific surface area and the dominant crystal plane (020), which was beneficial for ion exchange adsorption of tetracycline. For photocatalytic degradation, the introduced Fe (Fe3+/Fe2+ redox pathway) acted as the reaction sites for molecular oxygen activation and as the enrichment sites for photogenerated electrons, leading to a lower recombination rate of photogenerated electrons and holes. With the influence of Fe doping, more ∙O2- (approximately 1.8 times) were produced for degradation. This study clarified the mechanism of Fe doping on pollutant adsorption and molecular oxygen activation for bismuth-rich materials, as well as a reference for antibiotic removal via adsorption coupling degradation.

A theoretical simulation of carbon dioxide adsorption capture on amine-functionalized graphene oxides

Amine-functionalized graphene oxides (AFGOs) are potential candidates for CO2 capture applications, as the amine functional groups could act as effective sites, promoting CO2 adsorption strength and selectivity. However, the CO2 adsorption mechanism on AFGO appears to be ambiguous, particularly with no explicit identification of the chemically bonded species. In this work, density functional theory and microkinetic simulations were carried out to investigate the physical and chemical adsorption mechanisms and behavior between AFGO and CO2. Our findings indicate that the van der Waals and hydrogen bonding (HB) interactions constitute physical binding modes between the aminated GO and CO2. The chemical adsorption pathways on AFGO materials have been revealed by the transition state search method, in which the relevant CO2 adsorption species, including carbamic acid and carbamate, and their formation conditions were theoretically identified on AFGOs. The chemisorption mechanisms have been recognized to be the nucleophilic interaction between GO-supported amines and CO2, simultaneously assisted by the cooperative effect of multiple HB interactions. More specifically, the surface hydroxyl groups and water molecules can serve as proton transfer media and offer HB interactions, thus regulating the reaction activity and chemical adsorption species. This theoretical work presents a new insight into CO2-AFGO interaction mechanisms, which is valuable for designing aminated GO adsorbents.

Extent of As(III) versus As(V) adsorption on iron (oxyhydr) oxides depends on the presence of vacancy cluster-like micropore sites: Insights into a seesaw effect

Iron (oxyhydr)oxides are ubiquitous in terrestrial environments and play a crucial role in controling the fate of arsenic in sediments and groundwater. Although there is evidence that different iron (oxyhydr)oxides have different affinities towards As(III) and As(V), it is still unclear why As(V) adsorption on some iron (oxyhydr)oxides is larger than As(III) adsorption, while it is opposite for other ones. In this study, six typical iron (oxyhydr)oxides are selected to evaluate their adsorption capacities for As(III) and As(V). The characteristics of these iron minerals such as morphology, arsenic adsorption species, and pore size distribution are carefully examined using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), positron annihilation lifetime (PAL) spectroscopy, and X-ray absorption spectroscopy (XAS). We confirm a seesaw effect occurred in different iron minerals for As(III) and As(V) immobilization, i.e., at pH 6.0, adsorption of As(V) on hematite (0.73 μmol m−2) and magnetite (0.33 μmol m−2) is higher than for As(III) (0.61 μmol m−2 and 0.27 μmol m−2, respectively), for goethite and lepidocrocite it is almost equal, while As(III) sorption on ferrihydrite (5.77 μmol m−2) and schwertmannite (28.41 μmol m−2) showed higher sorption than As(V) (1.53 μmol m−2 and 12.99 μmol m−2, respectively). PAL analysis demonstrates that ferrihydrite and schwertmannite have a large concentration of vacancy cluster-like micropores, significantly more than goethite and lepidocrocite, followed by hematite and magnetite. The difference of adsorption of As(III) and As(V) to different iron (oxyhydr)oxides is due to differences in the abundance of vacancy cluster-like micropore sites, which are conducive for smaller size As(III) immobilization but not for larger size of As(V). The findings of this study provide novel insights into a seesaw effect for As(III) and As(V) immobilization on naturally occurring iron mineral.

Synergistic catalysis in Pd/La-CeO2 enhanced CH4 oxidation: The role of water and reactive oxygen species

The catalytic oxidation of methane (CH4) stands as an essential strategy for curtailing greenhouse gas emissions. This study advances CH4 oxidation using Pd on La-doped CeO2, where water (H2O) boosts oxidation efficiency. The temperature for obtaining 50 % CH4 conversion on Pd/La-CeO2 catalyst was reduced from 288 °C (without H2O) to 260 °C (with H2O), while that on CeO2 was 570 °C both under conditions with and without H2O. Operando DRIFTS analysis reveals the reaction pathway and intermediates during CH4 oxidation. Ce cations provide adsorption sites for CH4, leading to the generation of CH3 adsorbed species with the help of surface O2–. La doping creates oxygen vacancies essential for oxygen activation and foster the formation of reactive hydroxide (OH) from adsorbed H2O and O. Pd contributes to the formation of more reactive oxygen species that facilitate OH generation at La cations and the oxidation of CH4 adsorption species to CO2 and H2O. The synergistic interplay between Pd and La-CeO2 is particularly noteworthy, with H2O also playing a role in the gasification of surface carbonates, thereby enhancing the overall performance of CH4 oxidation. A kinetic model based on the Langmuir-Hinshelwood mechanism is proposed, offering an insight into CH4 oxidation.

Tuning Mg Doping and Features of Bone-like Apatite Nanoparticles Obtained via Hydrothermal Synthesis.

Nanocrystalline apatites have been intensively studied for decades, not only for their well-known mimesis of bone apatite but also for applicative purposes, whether as biomaterials for skeletal repair or more recently for a variety of nanomedical applications enabled by their peculiar surface characteristics. Particularly, ion-doped apatites are of great interest because the incorporation of foreign ions in the composition of apatite (nano)crystals alters the bulk and surface properties, modifying their ability to interact with the external environment. This is clearly seen in the physiology of bone tissue, whose mineral phase, a low crystallinity apatitic phase, can dynamically exchange ions with cells, thus driving bone metabolism. Taking bone mineral as a model, the present work describes the development of Mg-doped hydroxyapatite nanoparticles, exploiting hydrothermal synthesis to achieve extents of Mg2+ doping hardly achieved before and using citrate to develop stable apatite colloidal dispersions. Morphological and physicochemical analyses, associated with in-depth investigation of ions populating the apatitic lattice and the nonapatitic surface layer, concurred to demonstrate the cooperative presence of Mg2+ and citrate ions, affecting the dynamic ion retention/release mechanisms. Achieving high Mg2+ doping rates and understanding how Mg doping translates into surface activation of apatite-based nanoparticles is expected to foster the design of novel smart and tunable devices, to adsorb and release ionic species and cargo molecules, with potential innovations in the biomedical field or even beyond, as in catalysis or for environmental remediation.

Boosted adsorption and oxidation performances in peroxymonosulfate (PMS)-based heterogeneous fenton-like reactions via P, N co-doping strategy

The heterogeneous Fenton-like reactions (HTFR) have attracted considerable interest for their efficacy in degrading pollutants. However, the development of effective strategies for enhancing performance in HTFR remains a subject of ongoing research. Herein, a synergistic adsorption and oxidation-dominated process was developed to overcome the bottlenecks of peroxymonosulfate (PMS)-based HTFR in terms of mass transfer and catalyst reactivity. Heteroatom (P, N) co-doping for manganese (Mn) was employed to fabricate an efficient catalyst, Mn@5-NPC-800, which exhibited exceptional abilities of adsorption and PMS activation. The enhanced performance of HTFR was attributed to the increased specific surface area (SSA) and enhanced yields of graphitic-N/MnIII of the catalyst, which facilitated reactant enrichment and electron transfer in the delocalized conjugated area, respectively. The PMS-based HTFR induced by Mn@5-NPC-800 for pollutant removal was characterized by a synergistic adsorption and reactive oxygen species (ROS)-dominated oxidation process. DFT calculations revealed that the N, P co-doped carbon matrix (NPC) acted as a conductive bridge, significantly improving electron transfer between MnP and PMS molecule, which was identified as a key factor in governing the catalytic performance. The investigation presents a suggestive example of employing a doping strategy to create a synergistic effect of adsorption and oxidation, thereby strengthening the performance of Fenton-like reactions.

Ultrathin WO3 Nanosheets/Pd with Strong Metal-Support Interactions for Highly Sensitive and Selective Detection of Mustard-Gas Simulants.

Exposure to mustard gas can cause damage or death to human beings, depending on the concentration and duration. Thus, developing high-performance mustard-gas sensors is highly needed for early warning. Herein, ultrathin WO3 nanosheet-supported Pd nanoparticles hybrids (WO3 NSs/Pd) are prepared as chemiresistive sulfur mustard simulant (e.g., 2-chloroethyl ethyl sulfide, 2-CEES) gas sensors. As a result, the optimal WO3 NSs/Pd-2 (2 wt % of Pd)-based sensor exhibits a high response of 8.5 and a rapid response/recovery time of 9/92 s toward 700 ppb 2-CEES at 260 °C. The detection limit could be as low as 15 ppb with a response of 1.4. Moreover, WO3 NSs/Pd-2 shows good repeatability, 30-day operating stability, and good selectivity. In WO3 NSs/Pd-2, ultrathin WO3 NSs are rich in oxygen vacancies, offer more sites to adsorb oxygen species, and make their size close to or even within the thickness of the so-called electron depletion layer, thus inducing a large resistance change (response). Moreover, strong metal-support interactions (SMSIs) between WO3 NSs and Pd nanoparticles enhance the catalytic redox reaction performance, thereby achieving a superior sensing performance toward 2-CEES. These findings in this work provide a new approach to optimize the sensing performance of a chemiresistive sensor by constructing SMSIs in ultrathin metal oxides.

Understanding the Electronic and Structural Effects in ORR Intermediate Binding on Anion-Substituted Zirconia Surfaces.

For oxygen reduction reaction (ORR), the surface adsorption energies of O and OH* intermediates are key descriptors for catalytic activity. In this work, we investigate anion-substituted zirconia catalyst surfaces and determine that adsorption energies of O and OH* intermediates is governed by both structural and electronic effects. When the adsorption energies are not influenced by the structural effects of the catalyst surface, they exhibit a linear correlation with integrated crystal orbital Hamiltonian population (ICOHP) of the adsorbate-surface bond. The influence of structural effects, due to the re-optimisation slab geometry after adsorption of intermediate species, leads to stronger adsorption of intermediates. Our calculations show that there is a change in the bond order to accommodate the incoming adsorbate species which leads to stronger adsorption when both structural and electronic effects influence the adsorption phenomena. The insights into the catalyst-adsorbate interactions can guide the design of future ORR catalysts.

A multifunctional Er-MOF for Methylene Blue adsorption and CO2 cycloaddition catalysis

With the acceleration of industrialization and energy consumption, global concerns for the safety of ecological system and sequent human health have attracted consideration attention increasingly in view of the severe contamination both in aqueous environment and aerosphere. Therefore, the development of multifunctional species for efficient adsorption of pollutants and chemical fixation of CO2 receives increasing attention. Herein, an anionic ErIII metal organic framework (Er-MOF) with large hexagonal channels, is obtained based on a benzene-spaced tetracarboxylate ligand, H4L (H4L = 1,4-bis(2′,2′′,6′,6′′-tetracarboxy-1,4′:4,4′′-pyridyl) benzene). Adsorption analysis indicates that Er-MOF behaves as an excellent adsorbent for selectively absorbing MB in water with a maximum adsorption capacity of 494.1 mg·g‒1. The adsorption mechanism could be a combination of size matching, electrostatic interaction, π···π stacking and hydrogen bonding. In addition, Er-MOF is demonstrated to be an efficient catalyst in the cycloaddition of CO2 with epoxides under mild conditions due to its excellent stability, substantial specific surface area, confined space and well-exposed Lewis acid/base sites. The findings presented herein had great significance for enriching the multifunctional lanthanide MOFs in environmental applications.

Adsorption of dimethylaluminum isopropoxide (DMAI) on the Al2O3 surface: A machine-learning potential study

Dimethylaluminum isopropoxide (DMAI) is attracting attention as an alternative precursor for atomic layer deposition (ALD) of aluminum oxide (Al2O3). However, the surface chemical reaction mechanisms of DMAI during ALD regarding its dimeric structure under vacuum deposition process conditions has yet to be clear. In this work, the adsorption mechanism of dimeric and monomeric DMAI on a fully hydroxylated Al2O3 surface is studied using machine-learning potential (MLP) calculations. The initial adsorption of DMAI appears facile and would result in the coexistence of both methyl and isopropoxy ligands on the surface. The reactivity of DMAI is smaller than that of TMA, owing to the propensity of DMAI to adopt a dimeric form. Especially when the substrate is partially covered by other adsorbate species, the large molecular size and low reactivity of dimeric DMAI considerably hinder its reactivity toward surface adsorption. Current results are in good correspondence with the previous experimental results, where lower growth per cycle (GPC) and higher selectivity in area-selective ALD (AS-ALD) could be observed by using DMAI than compared to those of TMA processes.

Ion-Exchange Resin/Carrageenan-Copper-Based Nanocomposite: Artificial Neural Network, Advanced Thermodynamic Profiling, and Anticoagulant Studies.

Carrageenan (CG) and ion exchange resins (IERs) are better metal chelators. Kappa (κ) CG and IERs were synthesized and subjected to copper ion (Cu2+) adsorption to obtain DMSCH/κ-Cu, DC20H/κ-Cu, and IRP69H/κ-Cu nanocomposites (NCs). The NCs were studied using statistical physics formalism (SPF) at 315-375 K and a multilayer perceptron with five input nodes. The percentage of Cu2+ uptake efficiency was used as an outcome variable. Via the grand canonical ensemble, SPF gives models for both monolayer and multilayer sorption layers. For in vitro anticoagulant activity (ACA), the activated partial thromboplastin time were calculated using 100 μL of rabbit plasma incubated at 37 °C. After 2 min, 100 L of 0.025 M CaCl2 was added, and the clotting time was recorded for each group (n = 6). The results demonstrated that the key covariables for the adsorption process were pH and concentration. The results of artificial neural network models were comparable with the experimental findings. The error rates varied between 4.3 and 1.0%. The prediction analysis results ranged from 43.6 to 89.2. The ΔG and ΔS values for IRP69H/κ-Cu obtained were -18.91 and -16.32 and 26.21 and 22.74 kJ/mol for the temperatures 315 and 345 K, respectively. Adsorbate species were perpendicular to the adsorbent surfaces, notwithstanding the apparent importance of macro- and micropore volumes. These adsorbents typically fluctuate with temperature changes and contain one or more layers of sorption. Negative and positive sorption energies correspond to endothermic and exothermic processes. The biosorption energy (E1 and E2) values in this experiment have a value of less than 23 kJ mol-1. Complex SPF models' energy distributions validate surface properties and interactions with adsorbates. At a concentration of 100 μg/mL, DC20H/κ-Cu2+ exhibited an ACA of only 8 s. These NCs demonstrated better greater ACA with the order DC20H/κ < DMSCH/κ < IRP69H/κ. More research is needed to rule out the chemical processes behind the ACA of CG/IER-Cu NCs.

Tuning the coordination environment of sulfur on carbon surface via doping with iron for high-capacity gaseous elemental mercury capture

Enhancement of the formation of unsaturated short-chain sulfur represents the key point in enhancing the gaseous elemental mercury (Hg0) capture by sulfur-based sorbents, and yet the sulfur often agglomerates into long-chain species. Herein, by doping with iron cation as the regulator of the coordination environment of sulfur, the long-chain sulfur was successfully converted into short-chain sulfur on carbon. The iron-sulfur loaded carbon shows a high Hg0 adsorption capacity of 72.8 mg·g−1 (80 % breakthrough) and a low cost of $42.09/kg Hg, which are superior to various sulfur modified carbons and metal sulfides. The iron can not only immobilize more amount of sulfur on carbon surface, but also break the S-S bonds. The double interaction of iron and carbon with sulfur facilitates the formation of short-chain sulfur species for Hg0 adsorption. Density functional calculations suggest that S, Fe and C sites on surface are active centers for Hg adsorption. The Hg can tri-coordinate with S, Fe and C sites, which gives a high adsorption energy of − 219.3 kJ‧mol−1, confirming the strong reaction. This work provides a new in insights into the regulation of the coordination environment of sulfur, which allows the designing of high-capacity and low-cost sorbents for gaseous Hg0 removal.