High Surface Area Research Articles

Metal-Organic Framework Templated Z-Scheme ZnIn2S4/Bi2S3 Hierarchical Heterojunction for Photocatalytic H2O2 Production from Wastewater.

Metal-organic framework derived materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this work, a Z-scheme ZnIn2S4/Bi2S3 hierarchical heterojunction is first developed by a one-pot method using CAU-17 as a template. The specific preparation method endows an intimate interface contact between these two monomers, and CAU-17-derived Bi2S3 possesses a high surface area and porosity, resulting in an efficient charge separation and O2 capture. Thus, for photocatalytic H2O2 production from the O2 reduction reaction, the ZnIn2S4/Bi2S3 heterojunction can achieve an H2O2 yield of 995µmolL-1 in pure water and ambient air under visible light, 4.5 and 4 times that of ZnIn2S4 and Bi2S3, respectively. In addition, in tetracycline solution, ZnIn2S4/Bi2S3 can degrade tetracycline with a degradation rate of 95% by photocatalysis, and at the same time, a final H2O2 production yield of 1223µmolL-1 is reached. Similarly, high yields of H2O2 are also obtained from wastewater containing o-nitrophenol, acid golden yellow, or acid red, and these pollutants are effectively degraded. This work reveals the potential of metal-organic framework-derived materials in photocatalysis, as well as provides insights into H2O2 green synthesis and wastewater treatment.

Resistive gas sensors for the detection of NH3 gas based on 2D WS2, WSe2, MoS2, and MoSe2: A review.

Transition metal dichalcogenides (TMDs) with a two-dimensional (2D) structure and semiconducting features are highly favorable for the production of NH3 gas sensors. Among the TMD family, WS2, WSe2, MoS2, and MoSe2 exhibit high conductivity and a high surface area, along with high availability, reasons for which they are favored in gas-sensing studies. In this review, we have discussed the structure, synthesis, and NH3 sensing characteristics of pristine, decorated, doped, and composite-based WS2, WSe2, MoS2, and MoSe2 gas sensors. Both experimental and theoretical studies are considered. Furthermore, both room temperature and higher temperature gas sensors are discussed. We also emphasized the gas-sensing mechanism. Thus, this review provides a reference for researchers working in the field of 2D TMD gas sensors.

On the CO2 Harvesting from N2 Using Grazyne Membranes.

Separation of carbon dioxide (CO2) from nitrogen (N2) is central to any global warmingremediation technology aimed at reducing atmospheric CO2 content. Chemicalmembranes designed to differentially permeate both molecules are appealing due totheir simple use, being environmentally friendly, with high surface areas, compact,easy to maintain and cost-effective, still, the field is growing due to the difficulties inCO2/N2 separation. The present study poses grazynes, two-dimensional stripe-basedC-based materials with sp and sp2 C atoms, as suited membranes for CO2/N2separation. The combination of density functional theory and molecular dynamicssimulations allow tackling the energetics, kinetics, and dynamics of the membraneeffectiveness of pore-engineered grazynes in a holistic fashion. The explored grazynesare capable of physisorbing CO2 and N2, thus avoiding material poisoning bymolecular decoration, while the diffusion of CO2 through the pores is found to be rapid,yet easier than that of N2, in the rate order of the s-1 in the 100-500 K temperaturerange. In particular, low-temperature CO2 separation even for CO2 contents below0.5% are found for [1],[2]{2}-grazyne when controlling the membrane exposure contactto the gases mixture, paving the way for exploring and using grazynes for air CO2remediation.

Synthesis and characterization of hydroxyapatite nanoparticles from calcium hydroxide fouled with gases evolved from smokestack of glass industry

In glass industry, the evolved gases and fumes from burning the gas fuel absorbed in calcium hydroxide to minimize the pollution of environment. After a period of time, the calcium hydroxide fouled with sulphate and carbonate as action of the absorbed SO3 and CO2 gases. Based on our interest to treatment the solid waste materials, this study intended to convert the obtained waste of calcium hydroxide fouled with gases to valuable products. Firstly, this waste was treated with water, caustic soda and acids. The results confirmed the conversion of waste to pure calcium sulfate by treatment with 6 v/v% sulfuric acid. Secondly, the obtained calcium sulfate was reacted with ammonium dihydrogen phosphate solution for preparation of calcium hydroxyapatite (HAp) nanoparticles. The produced HAp sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and N2 adsorption measurements. The obtained findings confirmed that the HAp can be produced after calcination at 700 °C, nanorods-like of sizes ranged from 11 to 15 nm and with main surface functional groups of hydroxyapatite. TGA and DTA data indicated that HAp is thermally stable up to 700 °C. Also, the obtained HAp has Ca/P molar ratio of 1.60 and exhibited high total surface area of 146 m2/g with mesoporous structure which make this material can be used in medical and water purification applications.

Hierarchical porous carbon materials for lithium storage: Preparation, modification, and applications.

Secondary battery as an efficient energy conversion device have been highly attractive for alleviating the energy crisis and environmental pollution. Hierarchical porous carbon materials with multiple sizes pore channels are considered as promising materials for energy conversion and storage applications, due to their high specific surface area and excellent electrical conductivity. Although many reviews have reported on carbon materials for different fields, systematic summaries about hierarchical porous carbon materials for lithium storage are still rare. In this review, we fist summarize the main preparation methods of hierarchical porous carbon materials, including hard template method, soft template method, and template-free method. The modification methods including porosity and morphology tuning, heteroatom doping, and multiphase composites are introduced systematically. Then, the recent advances in hierarchical porous carbon materials on lithium storage are summarized. Finally, we outline the challenges and future perspectives for the application of hierarchical porous carbon materials in lithium storage.

Lead (Pb) Sorption Kinetics by Clay Minerals: Bentonite and Zeolite

Background: Heavy metal pollution chiefly lead (Pb) causes various environmental disequilibrium and health hazards. Immobilization of lead (Pb) usingclay minerals is cost effective for metal remediation due to their higher surface area and negative charges. Methods: This study was taken up to assess the Pb removal potentials of bentonite and zeolite from contaminated water and to study the effect of sorbent dosage, initial Pb2+ concentrations and incubation time intervals on Pb adsorption and desorption was studied. Result: Zeolite was effective in immobilising Pb (78.0%) than bentonite (70.9%) which increased with increasing sorbent dosage and time intervals. The pseudo second-order kinetic model described the Pb adsorption precisely. Chemisorption was the dominant mechanism operating in aqueous solution system, hence, it could be concluded that zeolite can be utilized as an efficient sorbent for wastewater treatment.

MOFs-Based Materials with Confined Space: Opportunities and Challenges for Energy and Catalytic Conversion.

Metal-Organic Frameworks (MOFs) are a very promising material in the fields of energy and catalysis due to their rich active sites, tunable pore size, structural adaptability, and high specific surface area. The concepts of "carbon peak" and "carbon neutrality" have opened up huge development opportunities in the fields of energy storage, energy conversion, and catalysis, and have made significant progress and breakthroughs. In recent years, people have shown great interest in the development of MOFs materials and their applications in the above research fields. This review introduces the design strategies and latest progress of MOFs are included based on their structures such as core-shell, yolk-shell, multi-shelled, sandwich structures, unique crystal surface exposures, and MOF-derived nanomaterials in detail. This work comprehensively and systematically reviews the applications of MOF-based materials in energy and catalysis and reviews the research progress of MOF materials for atmospheric water harvesting, seawater uranium extraction, and triboelectric nanogenerators. Finally, this review looks forward to the challenges and opportunities of controlling the synthesis of MOFs through low-cost, improved conductivity, high-temperature heat resistance, and integration with machine learning. This review provides useful references for promoting the application of MOFs-based materials in the aforementioned fields.

One-pot synthesis of NiCo-phyllosilicate supported on zeolite for enhanced degradation of antibiotic contaminants

The overuse of antibiotics currently results in the presence of various antibiotics being detected in water bodies, which poses potential risks to human health and the environment. Therefore, it is highly significant to remove antibiotics from water. In this study, we developed novel rod-like NiCo-phyllosilicate hybrid catalysts on calcined natural zeolite (NiCo@C-zeolite) via a facile one-pot process. The presence of the zeolite served as both a silicon source and a support, maintaining a high specific surface area of the NiCo@C-zeolite. Remarkably, NiCo@C-zeolite exhibited outstanding catalytic performance in antibiotic degradation under PMS activation. Within just 5 min, the degradation rate of metronidazole (MNZ) reached 96.14%, ultimately achieving a final degradation rate of 99.28%. Furthermore, we investigated the influence of catalyst dosage, PMS dosage, MNZ concentration, initial pH value, and various inorganic anions on the degradation efficiency of MNZ. The results demonstrated that NiCo@C-zeolite displayed outstanding efficacy in degrading MNZ under diverse conditions and maintained a degradation rate of 94.86% at 60 min after three consecutive cycles of degradation. Free radical quenching experiments revealed that SO•− 4 played a significant role in the presence of NiCo@C-zeolite-PMS system. These findings indicate that the novel rod-like NiCo-phyllosilicate hybrid catalysts had excellent performance in antibiotic degradation.

Freeze-Dryable, Stable, and Click-Reactive Nanoparticles Composed of Cello-oligosaccharides for Biomolecular Sensing.

Nanoparticles have been widely used as platforms for biomolecular sensing because of their high specific surface area and attractive properties depending on their constituents and structures. Nevertheless, it remains challenging to develop nanoparticulate sensing platforms that are easily storable without aggregation and conjugatable with various ligands in a simple manner. Herein, we demonstrate that nanoparticulate assemblies of cello-oligosaccharides with terminal azido groups are promising candidates. Azidated cello-oligosaccharides can be readily synthesized via the enzyme-catalyzed oligomerization reaction. This study characterized the assembled structures of azidated cello-oligosaccharides produced during the enzymatic synthesis and revealed that the terminal azidated cello-oligosaccharides formed rectangular nanosheet-shaped lamellar crystals. The azido groups located on the nanosheet surfaces were successfully exploited for antigen conjugation via the click chemistry. The resultant antigen-conjugated nanosheets allowed for the quantitative and specific detection of a corresponding antibody, even in 10% serum, owing to the antifouling properties of cello-oligosaccharide assemblies against proteins. It was found that the functionalized nanosheets were redispersible in water after freeze-drying. This remarkable characteristic is attributed to the well-hydrated saccharide residues on the nanosheet surfaces. Moreover, the antibody detection capability did not decline after the thermal treatment of the functionalized nanosheets in a freeze-dried state. Our findings contribute to developing convenient nanoparticulate biomolecular sensing platforms.

Correlating Electrolyte Infiltration with Accessible Surface Area in Macroporous Electrodes using Neutron Radiography

Abstract Carbon-based porous electrodes are commonly employed in electrochemical technologies as they provide a high surface area for reactions, an open structure for fluid transport, and enable compact reactor architectures. In electrochemical cells that sustain liquid electrolytes (e.g., redox flow batteries, CO2 electrolyzers, capacitive deionization), the nature of the interaction between the three phases - solid, liquid and gas - determines the accessible surface area for reactions, which fundamentally determines device performance. Thus, it is critical to understand the correlation between the electrolyte infiltration in the porous electrode and the resulting accessible surface area in realistic reactor architectures. To tackle this question, here we simultaneously perform neutron radiography with electrochemical measurements to correlate macroscopic electrode saturation/wetting with accessible surface area. We find that for untreated electrodes featuring neutral wettability with water, the electrode area remains underutilized even at elevated flow rates, both for interdigitated and parallel flow fields. Conversely, increasing the electrode hydrophilicity results in an order-of-magnitude increase in accessible surface area at comparable electrode saturation, and is less influenced by the electrolyte flow rate. Ultimately, we reveal useful correlations between reactor architectures and electrode utilization and provide a method that is broadly applicable to flow electrochemical reactors.

Design of highly efficient 0D/1D TiO2 photoanode for dye-sensitized solar cells by simple TiCl4 pre-treatment of titanate nanotubes

Dye-sensitized solar cells (DSCs) represent a promising avenue for sustainable energy conversion, with the efficiency of these devices heavily reliant on the performance of the TiO2 photoanode. Despite significant advancements, optimizing the photoanode material for higher efficiency remains a challenge. This study introduces a novel approach to constructing a highly efficient, multifunctional 0D/1D TiO2 composite by simply pre-treating the TiO2 precursor, specifically one-dimensional (1D) H-titanate nanotubes, with TiCl4. The TiCl4 treatment not only encourages the extensive synthesis of the one-dimensional nanostructures (i.e., nanorods) but also facilitates the in situ hydrolysis to generate small crystals that attach to the surface of the nanorods. The TiO2 composite offers several essential benefits, including the expanded thickness, high surface area for superior dye adsorption, efficient diffuse light scattering induced by the aggregate structures, and fast charge transport within the film matrix, making it an exemplary component for DSCs. The photovoltaic performance test revealed that TiCl4 pre-treatment increased power conversion efficiency by 36.3 %, rising from 7.63 % of untreated cells to a striking value of 10.4 %, which is a new record when N719 is used as a sensitizer and iodide-based redox shuttle employed as an electrolyte. This research provides an effective strategy for developing highly efficient photoanode material for DSCs.

Preparation and Investigation of High Surface Area Aerogels from Crosslinked Polypropylenes

Polypropylene-based aerogels with high surface area have been developed for the first time. By chemical crosslinking of polypropylene with oligomeric capped-end amino compounds, followed by dissolution, thermally induced phase separation, and the supercritical CO2 drying process or freeze-drying method, the aerogels exhibit high specific surface areas up to 200 m2/g. Moreover, the silica-cage multi-amino compound was utilized in a similar vein for forming hybrid polypropylene aerogels. According to the SEM, the developed polypropylene-based aerogels exhibit highly porous morphology with micro-nanoscale structural features that can be controlled by processing conditions. Our simple and inexpensive synthetic strategy results in a low-cost, chemically resistant, and highly porous material that can be tailored according to end-use applications.

Antibacterial activity of high surface area zinc oxide nanoparticles for controlling black rot disease of Chinese kale

AbstractZinc oxide nanoparticles (ZnO NPs) are inorganic compounds listed as “generally recognized as safe” (GRAS) materials and have been used in plant production as well as for plant disease control. This study investigated the antibacterial efficacy of ZnO NPs with various surface areas against Xanthomonas campestris pv. campestris, assessed the effectiveness of ZnO NPs in controlling black rot disease in Chinese kale, and examined the influence of ZnO NPs application on soil bacterial communities. The results showed that ZnO NPs with high surface area effectively inhibited X. campestris pv. campestris by restraining growth and causing cell damage. Seed treatment and foliar spray application of high surface area ZnO NPs at 250 μg/mL significantly reduced the disease severity of black rot. Furthermore, in the greenhouse experiment, the soil bacterial communities in the treatment of plants applied with ZnO NPs did not differ from those in soil of nontreated plants. Therefore, ZnO NPs have the potential to serve as an alternative substance for plant disease management.

CO2-Based Stable Porous Metal-Organic Frameworks for CO2 Utilization.

The transformation of carbon dioxide (CO2) into functional materials has garnered considerable worldwide interest. Metal-organic frameworks (MOFs), as a distinctive class of materials, have made great contributions to CO2 capture and conversion. However, facile conversion of CO2 to stable porous MOFs for CO2 utilization remains unexplored. Herein, we present a facile methodology of using CO2 to synthesize stable zirconium-based MOFs. Two zirconium-based MOFs CO2-Zr-DEP and CO2-Zr-DEDP with face-centered cubic topology were obtained via a sequential desilylation-carboxylation-coordination reaction. The MOFs exhibit excellent crystallinity, as verified through powder X-ray diffraction and high-resolution transmission electron microscopy analyses. They also have notable porosity with high surface area (SBET up to 3688 m2 g-1) and good CO2 adsorption capacity (up to 12.5 wt %). The resulting MOFs have abundant alkyne functional moieties, confirmed through 13C cross-polarization/magic angle spinning nuclear magnetic resonance and Fourier transform infrared spectra. Leveraging the catalytic prowess of Ag(I) in diverse CO2-involved reactions, we incorporated Ag(I) into zirconium-based MOFs, capitalizing on their interactions with carbon-carbon π-bonds of alkynes, thereby forming a heterogeneous catalyst. This catalyst demonstrates outstanding efficiency in catalyzing the conversion of CO2 and propargylic alcohols into cyclic carbonates, achieving >99% yield at room temperature and atmospheric pressure conditions. Thus, this work provides a dual CO2 utilization strategy, encompassing the synthesis of CO2-based MOFs (20-24 wt % from CO2) and their subsequent application in CO2 capture and conversion processes. This approach significantly enhances overall CO2 utilization.

Superlative Porous Organic Polymers for Photochemical and Electrochemical CO2 Reduction Applications: From Synthesis to Functionality.

To mimic the carbon cycle at a kinetically rapid pace, the sustainable conversion of omnipresent CO2 to value-added chemical feedstock and hydrocarbon fuels implies a remarkable prototype for utilizing released CO2. Porous organic polymers (POPs) have been recognized as remarkable catalytic systems for achieving large-scale applicability in energy-driven processes. POPs offer mesoporous characteristics, higher surface area, and superior optoelectronic properties that lead to their relatively advanced activity and selectivity for CO2 conversion. In comparison to the metal organic frameworks, POPs exhibit an enhanced tendency toward membrane formation, which governs their excellent stability with regard to remarkable ultrathinness and tailored pore channels. The structural ascendancy of POPs can be effectively utilized to develop cost-effective catalytic supports for energy conversion processes to leapfrog over conventional noble metal catalysts that have nonlinear techno-economic equilibrium. Herein, we precisely surveyed the functionality of POPs from scratch, classified it, and provided a critical commentary of its current methodological advancements and photo/electrochemical achievements in the CO2 reduction reaction.

Enhanced photocatalytic activity of porous TiO2 containing C/P/K derived from grapefruit peel.

Grapefruit peel possesses a porous structure and a significant specific surface area. In this study, we introduce an innovative and eco-friendly approach for synthesizing porous TiO2. This was accomplished by employing grapefruit peel as a bio-template and tetrabutyl titanate as the precursor, utilizing a two-step rotary impregnation-calcination process. The TiO2 faithfully reproduced the structural characteristics of the grapefruit peel across different scales, simultaneously incorporating C, P, K elements from the original grapefruit peel into the final samples. The fabricated samples were analyzed using XRD, XPS, SEM, TEM, BET, and UV-vis DRS. The results showed that the TiO2 displays an anatase phase, and possesses a high specific surface area. The investigation of photocatalytic performance demonstrated that the CPK-TiO2-10 sample exhibited outstanding photocatalytic activity against Rhodamine B (RhB) solution, achieving complete degradation within 60 minutes. Additionally, the total organic carbon (TOC) removal rate reached 91.34% after 60 minutes of irradiation. The sample maintained a high degradation efficiency, even after five recycling cycles. This exceptional performance can be attributed to its porous structure, enriched with pores and a larger surface area, as well as the beneficial effects of doping with C, P, K elements in TiO2.

Attaining Substantially Enhanced Oxygen Evolution Reaction Rates on Ni Foam Catalysts in a Gas Diffusion Electrode Setup

Water electrolysis plays a central role in the transition to a fossil‐free society, but there are significant challenges to overcome in order to increase its availability on a large scale. Alkaline water electrolysis is a mature and scalable technology, although it has several disadvantages compared to electrolyzers working in acidic environments. In particular, the use of highly alkaline aqueous electrolytes can lead to corrosion, and the achieved current densities are relatively low. This study addresses the latter limitation by introducing a gas diffusion electrode (GDE) setup as a novel development tool that bridges the gap between research and practical applications in commercial devices such as fuel cells and electrolyzers. A high surface area Ni foam catalyst that can sustain exceptional oxygen evolution reaction (OER) current densities of up to 4 A cm−2 in a quasi‐steady‐state within our GDE setup operating in an alkaline environment is presented. The high performance of this Ni‐based benchmark catalyst is attributed to its deposition onto a mesh‐like porous transport layer (PTL) via hydrogen‐templated electrodeposition. This forms a porous foam‐like structure that augments the mass transport of the gaseous reactants at the GDE.

Synthesis of nitrogen and sulfur bi-doped carbon obtained from spent sapelli wood sawdust and polyhydric alcohol with improved catalytic activity for hydrogen evolution reaction

Developing an efficient water electrolysis system is an important solution for on the development of highly active, cost-effective, and stable electrocatalysts. Carbon-based metal-free catalysts are one of the promising candidates for this purpose. Herein, we present a facile strategy to synthesize and characterize nitrogen and sulfur co-doped porous carbon (NS-PC) from spent sapelli wood sawdust and polyhydric alcohol (xylitol) for efficient hydrogen evolution reaction (HER) in alkaline electrolyte. The resultant NS-PC metal-free catalyst exhibits porous structure, high surface areas and enhanced HER performance with lowest Tafel slope of 68.1 mV dec−1. The enhanced performance is due to the high porosity of carbonaceous material and co-existence of active species (N in the forms of graphitic-N, pyridinic-N, pyrrolic-N, and S in the forms of C–S–C) induced by the maximum carbon-carbon bond polarization, charge re-distribution in the carbon matrices with a synergistically HER activity. In addition, this work provides a versatile and effective strategy for synthetizing excellent carbon-based metal free catalysts from the low cost biowaste for large-scale production of hydrogen through HER.

Ultrasmall Inorganic Mesoporous Nanoparticles: Preparation, Functionalization, and Application.

Ultrasmall mesoporous nanoparticles (<50nm), a unique porous nanomaterial, have been widely studied in many fields in the last decade owing to the abundant advantages, involving rich mesopores, low density, high surface area, numerous reaction sites, large cavity space, ultrasmall size, etc. This paper presents a review of recent advances in the preparation, functionalization, and applications of ultrasmall inorganic mesoporous nanoparticles for the first time. The soft monomicelles-directed method, in contrast to the hard-template and template-free methods, is more flexible in the synthesis of mesoporous nanoparticles. This is because the amphiphilic micelle has tunable functional blocks, controlled molecule masses, configurations and mesostructures. Focus on the soft micelle directing method, monomicelles could be classified into four types, i.e., the Pluronic-type block copolymer monomicelles, laboratory-synthesized amphiphilic block copolymers monomicelles, the single-molecule star-shaped block copolymer monomicelles, and the small-molecule anionic/cationic surfactant monomicelles. This paper also reviews the functionalization of the inner mesopores and the outer surfaces, which includes constructing the yolkshell structures (encapsulated nanoparticles), anchoring the active components packed on the shell and building an asymmetric Janus architecture. Then, several representative applications, involving catalysis, energy storage, and biomedicines are presented. Finally, the prospects and challenges of controlled synthesis and large-scale applications of ultrasmall mesoporous nanoparticles in the future are foreseen.

Synthesis of Stable 2D Conductive Lanthanide Organic Frameworks (Lu‐HHTP) for High‐Performance Humidity Sensors

Two‐dimensional conductive metal‐organic frameworks (MOFs) featuring structural diversity and high porosity represent promising platforms for chemiresistive humidity sensing. The precise control of the structure of lanthanide‐based MOFs and an exploration of its impact on charge transport and sensing applications have consistently been focal points for researchers. In this study, we present the synthesis and characterization of Lu‐HHTP (HHTP = 2,3,6,7,10,11‐hexahydroxytriphenylene) as highly crystalline and conductive porous materials. The polymeric framework of Lu‐HHTP encompasses 1D hexagonal channels and exhibits interlayer π‐π stacking, resulting in a material with a high surface area and uniform rod‐like microstructure. Benefiting from its elevated electrical conductivity, the Lu‐HHTP‐based humidity sensor exhibited commendable sensing properties within the relative humidity range of 33% to 95% at room temperature (25°C), achieving a response value as high as 19 at 95% relative humidity. Furthermore, the sensor displayed superior repeatability, characterized by rapid response and recovery speeds in the presence of moisture. These findings indicate that Lu‐HHTP holds substantial promise as a material for humidity sensors.