Porous Support Materials Research Articles

Osmotic energy harvesting using acrylic acid hydrogel PET membrane

In this study, we investigated the osmotic energy harvesting using a cation-selective membrane. The cation-selective membrane was synthesized by the incorporation of acrylic acid hydrogel in a porous support membrane. FTIR analysis and SEM images confirmed the presence of the acrylic acid hydrogel rods inside the porous support material. The exposure of the acrylic acid hydrogel PET (AP) membrane to a concentration gradient culminated in the generation of electric power. The AP membrane was evaluated in regard to the following parameters: EDiff, Io, Pmax and t+. The maximum power obtained with the membrane was 1.10 μW at the 40-fold concentration gradient (test area∽ 100 mm2). Increasing the concentration gradient increased the power output. However, a decrease in power output was observed after a certain value of the concentration gradient. An enhancement in power output was noted as the fraction of acrylic acid within the membrane was augmented. Additionally, the cation transference number also increased owing to a high charge density and a reduction in the mesh size. The AP membrane was also investigated in acidic and basic media. The time-dependent study revealed the superior chemical stability of the AP membrane.

Rational solvent selection for the preparation of industrial monolithic supported liquid-phase (SLP) olefin hydroformylation catalyst

Heterogenisation of the hydroformylation (HyFo) process converting C4 olefins and syngas (CO/H2) to n-pentanal can substantially reduce its carbon footprint by simplifying downstream processing. Current upscaling efforts include constructing a pilot plant containing a Rh-diphosphite-stabilized supported liquid-phase (SLP) catalyst. The air-sensitive nature of the catalyst requires in-situ impregnation of the porous support material with the liquid phase components (Rh-precursor, ligand, stabiliser) entailing the use of large quantities of an organic solvent. Environment, health, and safety (EHS) as well as regulatory aspects prompt the search for an alternative to dichloromethane (DCM), which was used as standard solvent for lab-scale studies. To obtain alternatives to DCM, the replacement solvent methyl tert-butyl ether (MTBE) and in-silico screening of more than 5000 solvent candidates has been performed covering boiling points and solubility predictions by COSMO-RS as well as carcinogenicity- and mutagenicity predictions by quantitative structure–activity relationship (QSAR) models. The final list of solvent candidates contained unsaturated compounds (alkenes, alkynes) in addition to ether- and ester-functionalized​ solvents, which are typically recommended as DCM replacements. Sufficiently high solubilities of ligand and stabiliser to prepare the desired SLP catalyst were experimentally determined in the following solvents: methyl propionate (MP), dimethoxymethane (DMM), MTBE, tetrahydrofuran (THF) and DCM for benchmarking, and a monolithic SLP catalyst prepared with MTBE demonstrated to perform equally well in the HyFo reaction of 1-butene as the benchmark catalyst prepared using DCM solvent. Overall, the study demonstrates a practical approach for selecting solvents with a greener profile for making catalyst systems applicable for large-scale production.

Conversion of carbon dioxide in biogas into acetic acid by Clostridium thailandense immobilized on porous support materials

This study aimed to convert CO2 in biogas into acetic acid using immobilized Clostridium thailandense cells on various support materials, including activated carbon, expanded clay, and coir. Immobilized cells and free cells were evaluated for their CO2 conversion ability into acetic acid using H2 as an electron donor at an H2 to CO2 in biogas ratio of 2:1 (v/v), 30 °C, 150 rpm. Results showed that immobilized cells on activated carbon increased CH4 content to 96.9% (v/v), and acetic acid production to 15.65 mmol/L within 96 h. These values outperformed free cells. The activated carbon-immobilized cells could be reused two times without losing efficacy in the purification of biogas and acetic acid production. This work indicates that using the immobilized cells offers a sustainable approach to biogas upgrading, reducing the environmental footprint of biogas production by increasing its energy content and purity.

Innovative strategies for enhancing gas separation: Ionic liquid-coated PES membranes for improved CO2/N2 selectivity and permeance

As a cost-effective advancement in membrane technology, this study investigates the impact of PEG additive and CBT on the structural, stability, and gas permeance properties of PES-coated membranes, utilizing 1-dodecyl-3-methylimidazolium chloride ionic liquid ([DDMI][Cl] IL) as a carrier liquid. BET and FT-IR analyses highlight the significant enhancement in performance through the immobilization of pores with [DDMIM][Cl] IL. The investigation focuses on PES-M5-coated membranes, revealing excellent stability in finger-like pore structures prepared through direct immersion and nitrogen pressure immobilization. PES-M5-coated membranes with [DDMIM][Cl] IL via direct immersion experience lower weight loss than those coated using nitrogen pressure, with critical pressures at 1.4 and 1.25 bar, respectively. The study identifies PES-coated membranes, particularly PES-M25 (20.88 GPU) with macro-void pores and PES-M5 (29 GPU) with finger-like pores, exhibiting the highest CO2 permeance and CO2/N2 selectivity. As a cost-effective advancement in membrane technology, ionic liquids are employed in support membranes to enhance gas separation. Employing pure PES membranes with varying pore structures, created through the NIPS method, the study immobilizes [DDMI][Cl] IL in membrane pores through nitrogen pressure and direct immersion. Results underscore the successful application of porous support materials coated with ionic liquids for continuous CO2 and sulfur compound separation, showcasing competitive permeability and selectivity compared to traditional polymer membranes.

MXene-decorated bio-based porous carbon composite phase change material for superior solar-thermal energy storage and thermal management of electronic components

Energy storage technology based on phase change materials (PCM) can effectively solve the problem of poor energy utilization. However, PCM suffer from problems such as low thermal conductivity and easy leakage, which seriously hinder their application in fields such as thermal energy storage. To solve the above issues, this research prepared a series of novel composite PCM by immersing polyethylene glycol (PEG) into MXene-wrapped wood-based porous carbon support materials through a simple vacuum impregnation method. Specially, the balsa wood-derived porous carbon has excellent skeletal structure and hydrophilicity under 1000 °C carbonization temperature and delignification treatment. Further, the effect of MXene content on the properties of the composite PCM was systematically investigated. It was shown that the composite PCM (PDM-20) made within 20 mg/mL MXene dispersion had the best overall performance, with a significant increase in thermal conductivity up to 0.69 W m−1 K−1, the enthalpy efficiency and relative enthalpy efficiency values of 96.8 %/103.0 %, respectively, while the photo-thermal conversion efficiency reaching 90.1 %, which was much higher than that of the unmodified composite PCM. In addition, PDM-20 provided a remarkable delayed effect on the heating and cooling of electronic components. Therefore, PDM-20 prepared in this study has broad application prospects in heat storage, solar thermal absorption and heat management of electronic devices. Meanwhile, it also offers a new idea for the development and fabrication of green and environmentally friendly composite PCM.

Top-down vs. bottom-up synthesis of Ga–based supported catalytically active liquid metal solutions (SCALMS) for the dehydrogenation of isobutane

Supported catalytically active liquid metal solutions (SCALMS) catalysts consist of a liquid metal solution of an active metal (e.g., Pd, Rh, Pt, Ni) in a low melting metal (e.g., Ga, In, Sn) deposited on a porous support material. In the current study, we extend and optimize the recently developed top-down synthesis protocol (ultrasonication of gallium metal) to prepare GaPd, GaRh and GaPt SCALMS systems. We compare the morphological differences in the obtained catalyst materials achieved between this approach and the more traditional bottom-up synthesis protocol (in situ thermal decomposition of triethylamino-gallane complex) using electron microscopy. Moreover, the spatial distribution of the catalytically active material in the porous alumina support is evaluated using high resolution argon physisorption measurements. Both techniques strongly indicate that the bottom-up approach leads to a high degree of pore penetration while the gallium droplets are largely on the outer surface in case of the top-down method. Changes to the surface chemistry of the support were also investigated by means of NH3/CO2 temperature programmed desorption. All catalytic systems synthesized by the two synthesis methods, i.e., GaPd, GaRh and GaPt, were tested in a quartz, fixed-bed tubular reactor for isobutane dehydrogenation. All SCALMS materials, irrespective of their individual synthesis protocol, were significantly more active than their pure metal counterparts. The SCALMS catalyst prepared using the bottom-up approach showed initial productivity of 407gbutenes molM–1 min−1, 832gbutenes molM–1 min−1, and 963gbutenes molM–1 min−1 for the GaPd, GaRh and GaPt respectively. These values represent more than twice the initial activity obtained with the top-down synthesized counterparts. This activity difference can be explained by the analytically determined difference in liquid metal droplet size distribution.

An analytical model for the energy storage potential of phase change materials supported by polymeric colloidal aerogels

Effective thermal energy storage has become one of the well-recognized aspects of modern energy management. Phase change materials (PCMs) shape-stabilized in the porous structure of porous support materials are one of the candidates to reach stable and effective thermal energy storage. This study presents an analytical model for the prediction of thermal energy storage density and thermal conductivity of colloidal aerogels impregnated by a PCM (TCAP model). The TCAP model is a series-parallel model that combines the thermal conductivity of the structure of the supporting aerogel and the thermal characteristics of the impregnated PCM. To validate the model, a mesoporous resorcinol-formaldehyde aerogel with an average pore diameter of 5.2 nm is synthesized, and two types of polyethylene glycol PCMs (PEG600 and PEG2000) are impregnated into the porous structure of the supporting material. The results confirm that the TCAP model can accurately predict the thermal energy storage characteristics of the system in terms of energy storage rate and density. Based on parametric studies, the highest heat capacity that can be achieved in a resorcinol-formaldehyde aerogel/polyethylene glycol is 35 kJ/kg.k with a ΔT of 40 K. On the other hand, it can be predicted that when ΔT increases from 10 K to 20 K, the energy storage of the system will change in the range of 52 % to 74 %. Moreover, The TCAP model developed in this study can be used to design/optimize energy storage materials for various applications such as smart buildings, solar energy storage devices, environmental thermal management systems, wearable thermal management devices, and temperature control in electronics.

Recent Progress and Future Prospects of Laccase Immobilization on MOF Supports for Industrial Applications.

Laccase is a multicopper oxidoreductase enzyme that can oxidize organics such as phenolic compounds. Laccases appear to be unstable at room temperature, and their conformation often changes in a strongly acidic or alkaline environment, making them less effective. Therefore, rationally linking enzymes with supports can effectively improve the stability and reusability of native enzymes and add important industrial value. However, in the process of immobilization, many factors may lead to a decrease in enzymatic activity. Therefore, the selection of a suitable support can ensure the activity and economic utilization of immobilized catalysts. Metal-organic frameworks (MOFs) are porous and simple hybrid support materials. Moreover, the characteristics of the metal ion ligand of MOFs can enable a potential synergistic effect with the metal ions of the active center of metalloenzymes, enhancing the catalytic activity of such enzymes. Therefore, in addition to summarizing the biological characteristics and enzymatic properties of laccase, this article reviews laccase immobilization using MOF supports, as well as the application prospects of immobilized laccase in many fields.

A Highly Active Cobalt Catalyst for the General and Selective Hydrogenation of Aromatic Heterocycles.

Nanostructured earth abundant metal catalysts that mediate important chemical reactions with high efficiency and selectivity are of great interest. This study introduces a synthesis protocol for nanostructured earth abundant metal catalysts. Three components, an inexpensive metal precursor, an easy to synthesize N/C precursor, and a porous support material undergo pyrolysis to give the catalyst material in a simple, single synthesis step. By applying this catalyst synthesis, a highly active cobalt catalyst for the general and selective hydrogenation of aromatic heterocycles could be generated. The reaction is important with regard to organic synthesis and hydrogen storage. The mild reaction conditions observed for quinolines permit the selective hydrogenation of numerous classes of N-, O- and S-heterocyclic compounds such as: quinoxalines, pyridines, pyrroles, indoles, isoquinoline, aciridine amine, phenanthroline, benzofuranes, and benzothiophenes.

Catalytic ozonation of methylethylketone over porous Mn–Cu/HZSM-5

The catalytic ozonation of methylethylketone (MEK) was performed at the room temperature (25 °C) using the synthesized Mn and Cu-loaded zeolite (ZSM-5, SiO2/Al2O3 = 80) catalysts. The ZSM-5 zeolite was used as a porous support material due to the large surface area and high capacity for adsorption of volatile organic compounds. Since Mn and Cu-loaded zeolite catalysts were effective for the catalytic ozonation of VOCs such as MEK, according to the loaded concentration of Mn and Cu, there are four types of metal loaded ZSM5 catalysts synthesized [5 wt% Mn/ZSM-5, 5 wt% Cu/ZSM-5, 5 wt% Mn-1 wt% Cu/ZSM-5 (5Mn1CuZSM), and 5 wt% Cu-1 wt% Mn/ZSM-5]. The catalytic efficiency for the removal of MEK and ozonation using the different catalysts was also studied. Based on various experimental analysis processes, the characteristics of the synthesized catalysts were explored and the removal efficiencies of MEK and O3 together with the COx concentration generated from the destruction of MEK and O3 were explored. The results for the decomposition of MEK and O3 at the room temperature indicated that the Mn dominant ZSM-5 catalysts showed better efficiency for the conversion of MEK and O3. The 5 wt% Mn/ZSM-5 outweighed the rest of them for the removal of MEK while the 5Mn1CuZSM showed the best catalytic reactivity for the conversion of O3 and the CO2 selectivity. It was ascertained that during the reaction time of catalyst and reactants of 120 min the Mn dominantly deposited bimetallic catalyst, 5Mn1CuZSM, was determined as the most effective for the removal of MEK and O3 due to the high capability of production of Mn3+ species and more available adsorbed oxygen sites compared to the other catalysts. Finally, the durability measurement for the 5Mn1CuZSM catalyst was performed together with the produced CO and CO2 concentration for 420 min.

Pb(II) Removal from Aqueous Solutions by Adsorption on Stabilized Zero-Valent Iron Nanoparticles—A Green Approach

Nano zero-valent iron particles (nZVFe) are known as one of the most effective materials for the treatment of contaminated water. However, a strong tendency to agglomerate has been reported as one of their major drawbacks. The present study describes a green approach to synthesizing stabilized nZVFe, using biomass as a porous support material. Therefore, in the first step, biomass-derived activated carbon was prepared by thermochemical procedure from rice straw (RSAC), and then the RSAC-supported nZVFe composite (nZVFe–RSAC) was employed to extract Pb(II) from aqueous solution and was successfully synthesized by the sodium borohydride reduction method. It was confirmed through scanning electron microscopy (SEM) and X-ray diffraction (XRD) characteristics that the nZVFe particles are uniformly dispersed. Results of the batch experiments showed that 6 (g L−1) of this nanocomposite could effectively remove about 97% of Pb(II) ions at pH = 6 from aqueous solution. The maximum adsorption capacities of the RS, RSAC, and nZVFe–RSAC were 23.3, 67.8, and 140.8 (mg g−1), respectively. Based on the results of the adsorption isotherm studies, the adsorption of Pb(II) on nZVFe–RSAC is consistent with the Langmuir–Freundlich isotherm model R2=0.996). The thermodynamic outcomes exhibited the endothermic, possible, and spontaneous nature of adsorption. Adsorption enthalpy and entropy values were determined as 32.2 kJ mol−1 and 216.9 J mol−1 K−1, respectively. Adsorption kinetics data showed that Pb(II) adsorption onto nZVFe–RSAC was fitted well according to a pseudo-second-order model. Most importantly, the investigation of the adsorption mechanism showed that nZVFe particles are involved in the removal of Pb(II) ions through two main processes, namely Pb adsorption on the surface of nZVFe particles and direct role in the redox reaction. Subsequently, all intermediates produced through the redox reaction between nZVFe and Pb(II) were adsorbed on the nZVFe–RSAC surface. According to the results of the NZVFe–RSAC recyclability experiments, even after five cycles of recovery, this nanocomposite can retain more than 60% of its initial removal efficiency. So, the nZVFe–RSAC nanocomposite could be a promising material for permeable reactive barriers given its potential for removing Pb(II) ions. Due to low-cost and wide availability of iron salts as well as rice biowaste, combined with the high adsorption capacity, make nZVFe–RSAC an appropriate choice for use in the field of Pb(II) removal from contaminated water.

Predictive Modeling of Electrodeposition in a Single Pore Flow-Through Electrode: From Electronucleation to Coating Thickness Uniformity

The emergence of advanced manufacturing methods capable of producing porous three-dimensional structures has expanded the design space for next-generation functional components. The ability to fabricate ordered 3D foams for use in electrocatalysis reactors has increased the need for controlled deposition of catalytic metals onto porous support materials, such as carbon. However, there is a lack of clear design guidelines for electrodeposition onto 3D substrates, due to the geometric complexity and multi-scale nature of the problem. Furthermore, electro-nucleation phenomena are often overlooked in macro-scale models of current distribution during deposition. Here, a graphite flow-through electrode (FTE) is used as a model system for copper deposition within a single pore. Potential distributions and electro-nucleation phenomena are coupled in a continuum level model by incorporating nucleation size and density as a function of overpotential, determined experimentally using in situ atomic force microscopy (AFM). The model predictions are validated by measuring the coating uniformity in the pore using micro-computed X-ray tomography (μCT). A scaling analysis comprising dimensionless parameters such as the Wagner number is presented. The simplified scaling relationship framework can guide the electrodeposition process and electrode design to optimize plating of porous substrates under fluid flow conditions.

Influence of the ZnCrAl Oxide Composition on the Formation of Hydrocarbons from Syngas.

The conversion of syngas into value-added hydrocarbons gains increasing attention due to its potential to produce sustainable platform chemicals from simple starting materials. Along this line, the "OX-ZEO" process that combines a methanol synthesis catalyst with a zeolite, capable of catalyzing the methanol-to-hydrocarbon reaction, was found to be a suitable alternative to the classical Fischer-Tropsch synthesis. Hitherto, understanding the mechanism of the OX-ZEO process and simultaneously optimizing the CO conversion and the selectivity toward a specific hydrocarbon remains challenging. Herein, we present a comparison of a variety of ZnCrAl oxides with different metal ratios combined with a H-ZSM-5 zeolite for the conversion of syngas to hydrocarbons. The effect of aluminum on the catalytic activity was investigated for ZnCrAl oxides with a Zn/Cr ratio of 4:1, 1:1, and 1:2. The product distribution and CO conversion were found to be strongly influenced by the Zn/Cr/Al ratio. Although a ratio of Zn/Cr of 1:2 was best to produce lower olefins and aromatics, with aromatic selectivities of up to 37%, catalysts with a 4:1 ratio revealed high paraffin selectivity up to 52%. Notably, a distinct effect of aluminum in the oxide lattice on the catalytic activity and product selectivity was observed, as a higher Al content leads to a lower CO conversion and a changed product spectrum. We provide additional understanding of the influence of different compositions of ZnCrAl oxides on their surface properties and the catalytic activity in the OX-ZEO process. Furthermore, the variation of the zeolite component supports the important role of the channel topology of the porous support material for the hydrocarbon production. In addition, variation of the gas hourly space velocity showed a correlation of contact time, CO conversion, and hydrocarbon selectivity. At a gas hourly space velocity of 4200 mL/gcat h, CO conversion as high as 44% along with a CO2 selectivity of 42% and a lower paraffin (C2 0-C4 0) selectivity of 41% was observed.

Design of a graphene oxide@melamine foam/polyaniline@erythritol composite phase change material for thermal energy storage

At present, only a single modification method is adopted to improve the shortcomings of erythritol (ET) as a phase change material (PCM). Compared with a single modification method, the synergistic effect of multiple modification methods can endow ET with comprehensive performance to meet the purpose of package, supercooling reduction, and enhancement of thermal conductivity. In this work, we innovatively combine graphene oxide (GO) nanosheet modified melamine foam (MF) and polyaniline (PANI) to construct a novel ET-based PCM by blending and porous material adsorption modification. PANI as the nucleation center can enhance the crystallization rate, thereby reducing the supercooling of ET. Meanwhile, GO@MF foam can not only be used as a porous support material to encapsulate ET but also as a heat conduction reinforcement to improve heat storage and release rate. As a result, the supercooling of GO@MF/PANI@ET (GMPET) composite PCM decreases from 91.2 °C of pure ET to 57.9 °C and its thermal conductivity (1.58 W⋅m−1⋅K−1) is about three times higher than that of pure ET (0.57 W⋅m−1⋅K−1). Moreover, after being placed at 140 °C for 2 h, there is almost no ET leakage in the GMPET composite PCM, and the mass loss ratio is less than 0.75%. In addition, the GMPET composite PCM displays a high melting enthalpy of about 259 J⋅g−1 and a high initial mass loss temperature of about 198 °C. Even after the 200th cycling test, the phase transition temperature and the latent heat storage capacity of the GMPET PCM all remain stable. This work offers an effective and promising strategy to design ET-based composite PCM for the field of energy storage.

Design and direct preparation of a novel silicon carbide support for zeolite membrane

The support for the membrane is the basis for the preparation and application of the zeolite membrane. Moreover, its cost and properties directly determine the performance of the zeolite membrane and its industrial applications. A novel porous silicon carbide (SiC) support for zeolite membrane bonded with needle-like mullite (3Al2O3·2SiO2) was prepared using SiC powders as the raw material and kaolin, Al(OH)3, and AlF3 as the needle-like mullite precursor additives via an in situ high-temperature reactions in an air atmosphere. Effects of the support material composition and the sintering temperature on the sintering behavior, pore structure, permeability, and microstructure of the resultant supports were extensively investigated. The needle-like mullite formation consumed silicon oxide (SiO2) and generated a rigid skeleton structure with a good pore structure and bonding phase. Hence, the porous SiC support exhibited high porosity, with relatively large pore size and mechanical strength, which helped improve the support performance. Notably, the porous SiC support sintered at 1480 °C with in situ inter-particle needle-like mullite bonding exhibited excellent filtration and permeability performance. The porous support materials and methods used in this work are suitable for designing and preparing a novel porous SiC support for zeolite membranes.

Strong dual-metal-support interactions induced by low-temperature plasma phenomenon

Supported bimetallic nanoparticles have important industrial applications. However, the direct synthesis of intermetallic alloy nanocatalysts against sintering and aggregation on porous support materials via strong metal-support interactions (SMSIs) remains challenging. Herein, we report a novel synthesis strategy used to achieve low-temperature-plasma-induced SMSIs on a MgO-supported MAg (M = Cu, Fe, or Ni) system by focusing an electric field at a localized interface. The electric-field-controlled discharge plasma intrinsically promoted the formation of a porous MgO structure. This unique structure comprised partially encapsulated MAg nanoparticles (NPs) with a porous MgO layer and co-localized M and Ag NPs in close proximity. Owing to the uniform size distribution of the intermetallic NPs and the unique surface properties of the porous support, the resulting MAg@MgO catalysts exhibited high activity and excellent reusability toward the reduction of nitro and carbonyl groups. In particular, the conversion efficiency of CuAg@MgO (100% after 20 s) was significantly higher than that of the most commonly used catalysts; moreover, its activity did not decrease after 20 cycles of cinnamaldehyde hydrogenation. We believe that this synthesis route provides a universal method for designing and preparing high-activity supported metal catalysts.

Marginal lands as an important potential to produce biohydrogen

One of the promising approaches for hydrogen production is agricultural biomass crops conversion, which is a renewable-based clean and abundant resource. The main objective of the current study is to assess the contribution of soil beneficial microbes in improving salt tolerance along with the evaluation of possible hydrogen production from sorghum plant biomass. High salinity concentrations in soil stimulate plant roots to enhance the plant desire for symbiosis and association with vesicular-arbuscular mycorrhizal fungi (VAM). Among the VAM species, G.mosseae is one of the significant and effective VAM species, which contribute to plant salinity resistance by expanding leaf salt potential and accumulating nutrients leaves in comparison to other soil microorganisms in plants. Morphological characters of these plants show a higher biomass production during saline conditions up to 2000 kg/ha. Biomass production in the specific alternative thermochemical and biological processes are suggested and finally, gasification processes were chosen as the optimal method which can be practically applied to produce hydrogen from sorghum plants. By producing 10,000 kg biomass in three harvesting periods of Sorghum, almost 3000 kg biomass for bio-hydrogen production can be obtained. This could be an appropriate resource for obtaining biofuels, particularly bio-hydrogen from 3 million hectares of unbearable or poor quality lands in a country such as Turkey by producing 9 million tons of Hydrogen. Obtained data gives an overview of these technologies for hydrogen production from biomass yielding to 28.2 gH2/100 g biomass or 33.17 to 44.26 (gH2). Producing green hydrogen from plants biomass is relatively cheaper, compared to chemo-industrial methods. Achieving the immobilization factors in bioprocesses for microorganisms is obtained in this study. Consequently, hydrogen productivity of the bioprocess can be enhanced by using porous support materials which provide high biomass holding capacity and help better gas retrieve in the process.

Bridging Hydrometallurgy and Biochemistry: A Protein-Based Process for Recovery and Separation of Rare Earth Elements.

The extraction and subsequent separation of individual rare earth elements (REEs) from REE-bearing feedstocks represent a challenging yet essential task for the growth and sustainability of renewable energy technologies. As an important step toward overcoming the technical and environmental limitations of current REE processing methods, we demonstrate a biobased, all-aqueous REE extraction and separation scheme using the REE-selective lanmodulin protein. Lanmodulin was conjugated onto porous support materials using thiol-maleimide chemistry to enable tandem REE purification and separation under flow-through conditions. Immobilized lanmodulin maintains the attractive properties of the soluble protein, including remarkable REE selectivity, the ability to bind REEs at low pH, and high stability over numerous low-pH adsorption/desorption cycles. We further demonstrate the ability of immobilized lanmodulin to achieve high-purity separation of the clean-energy-critical REE pair Nd/Dy and to transform a low-grade leachate (0.043 mol % REEs) into separate heavy and light REE fractions (88 mol % purity of total REEs) in a single column run while using ∼90% of the column capacity. This ability to achieve, for the first time, tandem extraction and grouped separation of REEs from very complex aqueous feedstock solutions without requiring organic solvents establishes this lanmodulin-based approach as an important advance for sustainable hydrometallurgy.

Porous Materials Confining Single Atoms for Catalysis.

In recent years, single-atom catalysts (SACs) have received extensive attention due to their unique structure and excellent performance. Currently, a variety of porous materials are used as confined single-atom catalysts, such as zeolites, metal-organic frameworks (MOFs), or carbon nitride (CN). The support plays a key role in determining the coordination structure of the catalytic metal center and its catalytic performance. For example, the strong interaction between the metal and the carrier induces the charge transfer between the metal and the carrier, and ultimately affects the catalytic behavior of the single-atom catalyst. Porous materials have unique chemical and physical properties including high specific surface area, adjustable acidity and shape selectivity (such as zeolites), and are rational support materials for confined single atoms, which arouse research interest in this field. This review surveys the latest research progress of confined single-atom catalysts for porous materials, which mainly include zeolites, CN and MOFs. The preparation methods, characterizations, application fields, and the interaction between metal atoms and porous support materials of porous material confined single-atom catalysts are discussed. And we prospect for the application prospects and challenges of porous material confined single-atom catalysts.

Modified cellulose nanofibril aerogel: Tunable catalyst support for treatment of 4-Nitrophenol from wastewater

4-Nitrophenol (4-NP) is a hazardous aromatic compound widely used for various industries. Catalytic reduction of 4-NP using metal nanoparticles (NPs) is a highly effective method to treat 4-NP from waste effluent. Even though lots of methods have investigated to prepare efficient metal NPs composites, the nano and/or micro size of composites makes it hard to recover after wastewater treatment, limiting its practical use. Here, we fabricate 3-dimensional polyethylene imine grafted cellulose nanofibril (CNF-PEI) aerogel as a porous support material for platinum (Pt) NPs to practically and effectively treat 4-NP from wastewater. The Pt NPs are formed in-situ mode on cylindrical CNF-PEI aerogel by adsorption reaction with amine groups of PEI and subsequently reduction with NaBH4. Control of PEI grafting density and the initial concentration of Pt ions allows manipulation of the loading mass, size, and distribution of Pt NPs on 3D scaffold of CNF-PEI aerogel. The composite aerogel shows high catalytic activity for conversion of 4-NP. The 4-NP conversion activity is strongly affected by the size of Pt NPs and effective surface area of aerogels. The 2.74 nm size Pt NPs with even distribution in the aerogel show fast reaction kinetics (k = 0.12 min−1). Finally, 4-NP reduction efficiency does not decrease during 5 times reuse cycle of Pt NPs loaded CNF-PEI aerogel. This CNF-PEI aerogel loaded with Pt NPs is recovered easily from wastewater after treatment, so it is reusable and offers high potential as a practical recyclable environmental catalyst.