The enzymatic redox reactions in natural photosynthesis rely much on the participation of cofactors, with reduced nicotinamide adenine dinucleotide/nicotinamide adenine dinucleotide phosphate (NADH/NADPH) or their oxidized form (NAD+/NADP+) as an important redox power. The photocatalytic regeneration of expensive and unstable NADH/NADPH in vitro is an important process in enzymatic reduction and has attracted much research attention. Though different types of photocatalysts have been developed for photocatalytic NADH/NADPH regeneration, the efficiency is still relatively low. To elucidate the key factors affecting the performance of photocatalytic NADH/NADPH regeneration is helpful to rationally design the photocatalyst and improve the photocatalytic efficiency. In this paper, we overview the recent progress in photocatalytic NADH/NADPH regeneration with the focus on the strategies to improve the visible light adsorption, the charge separation and migration efficiency, as well as the surface reaction, which jointly determine the overall photocatalytic regeneration efficiency. The potential development of photocatalytic NADH/NADPH regeneration and photocatalytic-enzymatic-coupling system is prospected finally.
Extensive research efforts are currently devoted to developing and improving conventional technologies for water treatment. Membrane-based water treatment technologies are among the most preferred options due to their commercial success, simple operation, low energy and space requirements, and high separation efficiency. Despite the advances made in membrane-based technologies, fouling remains a critical challenge. Fouling occurs upon the accumulation of unwanted impurities on the membrane surface and within the membrane pores which results in a significant decline in the membrane permeate flux. To alleviate the operational challenges from fouling, surface modification to develop antifouling membranes appears to be an effective technique. A comprehensive review of the surface modification techniques for the development of antifouling membranes is provided in this paper. Chemical surface modification techniques (grafting and plasma treatment), physical modification techniques (blending, coating, adsorption, and thermal treatment), and combined physical and chemical modification techniques have been discussed. Moreover, the challenges related to surface modification and the future research directions are addressed.
Carbon dioxide fixation presents a potential solution for mitigating the greenhouse gas issue. During carbon dioxide fixation, C1 compound reduction requires a high energy supply. Thermodynamic calculations suggest that the energy source for cofactor regeneration plays a vital role in the effective enzymatic C1 reduction. Hydrogenase utilizes renewable hydrogen to achieve the regeneration and supply cofactor nicotinamide adenine dinucleotide (NADH), providing a driving force for the reduction reaction to reduce the thermodynamic barrier of the reaction cascade, and making the forward reduction pathway thermodynamically feasible. Based on the regeneration of cofactor NADH by hydrogenase, and coupled with formaldehyde dehydrogenase and formolase, a favorable thermodynamic mode of the C1 reduction pathway for reducing formate to dihydroxyacetone (DHA) was designed and constructed. This resulted in accumulation of 373.19 μmol·L–1 DHA after 2 h, and conversion reaching 7.47%. These results indicate that enzymatic utilization of hydrogen as the electron donor to regenerate NADH is of great significance to the sustainable and green development of bio-manufacturing because of its high economic efficiency, no by-products, and environment-friendly operation. Moreover, formolase efficiently and selectively fixed the intermediate formaldehyde (FALD) to DHA, thermodynamically pulled formate to efficiently reduce to DHA, and finally stored the low-grade renewable energy into chemical energy with high energy density.
Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction, which is a crucial half-reaction of overall water splitting. However, it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability. Herein, we report two-dimensional multifunctional layered double hydroxides derived from metal-organic framework sheet precursors supported by nanoporous gold with high porosity, which exhibit appealing performances toward oxygen/hydrogen evolution reactions, hydrazine oxidation reaction, and overall hydrazine splitting. The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm–2 toward oxygen evolution reaction. The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm–2, which is far more superior than that of the overall water splitting system (1.849 V). The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate, which could endow the sample with high surface area and excellent conductivity, resulting in superior activity and stability.
CO2 capture is one of the key technologies for dealing with the global warming and implementing low-carbon development strategy. The emergence of ionic metal-organic frameworks (I-MOFs) has diversified the field of porous materials, which have been extensively applied for gas adsorption and separation. In this work, amino-functionalized imidazolium ionic liquid as organic monodentate ligand was used for one step synthesis microporous Cu based I-MOFs. Precise tuning of the adsorption properties was obtained by incorporating aromatic anions, such as phenoxy, benzene carboxyl, and benzene sulfonic acid group into the I-MOFs via a facile ion exchange method. The new I-MOFs showed high thermal stability and high capacity of 5.4 mmol·g–1 under atmospheric conditions for selective adsorption of CO2. The active sites of microporous Cu-MOF are the ion basic center and unsaturated metal, and electrostatic attraction and hydroxyl bonding between CO2 and modified functional sulfonic groups are responsible for the adsorption. This work provides a feasible strategy for the design of I-MOF for functional gas capture.
To enhance the yields of benzene, toluene, and xylene in tetralin hydrocracking, the effect of the support acid properties of NiMo catalysts on hydrocracking performance of tetralin were investigated in this study. NaY zeolites were modified by hydrothermal treatment to form USY zeolites at different temperatures and adjust the type and amount of acid. In addition, H-Beta was loaded into the USY to further adjust the acidic properties of the catalysts. The result shows that when the total B acid content of the catalyst is maintained between 150 and 200 μmol·g–1, the total acid amount is maintained between 1.7 and 1.9 mmol·g–1, and the L/B (L and B acids) ratio is maintained between 1.5 and 2, the catalysts have favorable performances on tetralin hydrocracking. Under this condition, the catalysts have a yield of benzene, toluene, and xylene higher than 30 wt % and a selectivity for benzene, toluene, and xylene higher than 35%. The tetralin conversion is greater than 85 wt %. The AB6 catalyst obtains the best hydrocracking effect with the conversion of tetralin reaching 90.24 wt %, the yields of benzene, toluene, and xylene reaching 33.58 wt %, and the selectivity of benzene, toluene, and xylene reaching 37.21%, respectively.
Thallium is a highly toxic metal, and trace amount of thallium(I) (Tl+) in potable water could cause a severe water crisis, which arouses the exploitation of highly-effective technology for purification of Tl+ contaminated water. This report proposes the multi-layered Prussian blue (PB)-decorated composite membranes (PBx@PDA/PEI-FP) based on the aminated filter papers for Tl+ uptake. Extensively characterization by Fourier transform infrared spectrometer-attenuated total reflectance, scanning electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy and X-ray diffraction were performed to confirm the in situ growth of cubic PB crystals on filter paper membrane surfaces via the aminated layers, and the successful fabrication of multi-layered PB overcoats via the increasing of aminated layers. The effect of PB layers on Tl+ removal by PBx@PDA/PEI-FP from simulated drinking water was evaluated as well as the influence of different experimental conditions. A trade-off between PB decoration layer number and PB distribution sizes is existed in Tl+ uptake by PBx@PDA/PEI-FP. The double-layered PB2@PDA/PEI-FP membrane showed the maximum sorption capacity, but its Tl+ uptake performance was weakened by the acid, coexisting ions (K+ and Na+) and powerful operation pressure, during filtrating a large volume of low-concentrated Tl+-containing water. However, the negative effect of coexisting ions on the Tl+ uptake could be effectively eliminated in weak alkaline water, and the Tl+ removal was increased up to 100% without any pressure driving for PB2@PDA/PEI-FP membrane. Most importantly, PB2@PDA/PEI-FP displayed the high-efficiency and high-selectivity in purifying the Tl+-spiked Pearl River water, in which the residual Tl+ in filtrate was less than 2 μg·L–1 to meet the drinking water standard of United States Environmental Protection Agency. This work provides a feasible avenue to safeguard the drinking water in remote and underdeveloped area via the energy-free operation.
Ammonia is crucial in industry and agriculture, but its production is hindered by environmental concerns and energy-intensive processes. Hence, developing an efficient and environmentally friendly catalyst is imperative. In this study, we employed a straightforward and efficient impregnation technique to create various Cu-doped catalysts. Notably, the optimized 10Fe-8Cu/TiO2 catalyst exhibited exceptional catalytic performance in converting NO to NH3, achieving an NO conversion rate exceeding 80% and an NH3 selectivity exceeding 98% at atmospheric pressure and 350 °C. We employed in situ diffuse reflectance Fourier transform infrared spectroscopy and conducted density functional theory calculations to investigate the intermediates and subsequent adsorption. Our findings unequivocally demonstrate that Cu doping enhances the rate-limiting hydrogenation step and lowers the energy barrier for NH3 desorption, thereby resulting in improved NO conversion and enhanced selectivity toward ammonia. This study presents a pioneering approach toward energy-efficient ammonia synthesis and recycling of nitrogen sources.
Bifunctional metal/zeolite materials are some of the most suitable catalysts for the direct hydroalkylation of benzene to cyclohexylbenzene. The overall catalytic performance of this reaction is strongly influenced by the hydrogenation, which is dependent on the metal sizes. Thus, systematically investigating the metal size effects in the hydroalkylation of benzene is essential. In this work, we successfully synthesized Ru and Pd nanoparticles on Sinopec Composition Materials No.1 zeolite with various metal sizes. We demonstrated the size-dependent catalytic activity of zeolite-supported Ru and Pd catalysts in the hydroalkylation of benzene, which can be attributed to the size-induced hydrogen spillover capability differences. Our work presents new insights into the hydroalkylation reaction and may open up a new avenue for the smart design of advanced metal/zeolite bi-functional catalysts.
Decalin is considered as an important compound of high-energy-density endothermic fuel, which is an ideal on-board coolant for thermal management of advanced aircraft. However, decalin contains two isomers with a tunable composition, and their effects on the pyrolysis performance, such as the heat sink and coking tendency have not been demonstrated. Herein, we investigated the pyrolysis of decalin isomers, i.e., cis-decalin, trans-decalin and their mixtures (denoted as mix-decalin), in order to clarify the effects of the cis-/trans-structures on the pyrolysis performance of decalin fuels. The pyrolysis results confirmed that conversion of the tested fuels (600–725 °C, 4 MPa) decreased in the order cis-decalin > mix-decalin > trans-decalin. Detailed analyses of the pyrolysis products were used to compare the product distributions from cis-decalin, mix-decalin and trans-decalin, and the yields of some typical components (such as cyclohexene, 1-methylcyclohexene, benzene and toluene) showed significant differences, which could be ascribed to deeper cracking of cis-decalin. Additionally, the heat sinks and coking tendencies of the decalins decreased in the order cis-decalin > mix-decalin > trans-decalin. This work demonstrates the relationship between the cis/trans structures and the pyrolysis performance of decalin, which provides a better understanding of the structure-activity relationships of endothermic hydrocarbon fuels.
The widespread implementation of supercapacitors is hindered by the limited energy density and the pricey porous carbon electrode materials. The cost of porous carbon is a significant factor in the overall cost of supercapacitors, therefore a high carbon yield could effectively mitigate the production cost of porous carbon. This study proposes a method to produce porous carbon spheres through a spray drying technique combined with a carbonization process, utilizing renewable enzymatic hydrolysis lignin as the carbon source and KOH as the activation agent. The purpose of this study is to examine the relationship between the quantity of activation agent and the development of morphology, pore structure, and specific surface area of the obtained porous carbon materials. We demonstrate that this approach significantly enhances the carbon yield of porous carbon, achieving a yield of 22% in contrast to the conventional carbonization-activation method (9%). The samples acquired through this method were found to contain a substantial amount of mesopores, with an average pore size of 1.59 to 1.85 nm and a mesopore ratio of 25.6%. Additionally, these samples showed high specific surface areas, ranging from 1051 to 1831 m2·g−1. Zinc ion hybrid capacitors with lignin-derived porous carbon cathode exhibited a high capacitance of 279 F·g−1 at 0.1 A·g−1 and an energy density of 99.1 Wh·kg−1 when the power density was 80 kW·kg−1. This research presents a novel approach for producing porous carbons with high yield through the utilization of a spray drying approach.
Organic matter-induced mineralization is a green and versatile method for synthesizing hybrid nanostructured materials, where the material properties are mainly influenced by the species of natural biomolecules, linear synthetic polymer, or small molecules, limiting their diversity. Herein, we adopted dendrimer poly(amidoamine) (PAMAM) as the inducer to synthesize organosilica-PAMAM network (OSPN) capsules for mannose isomerase (MIase) encapsulation based on a hard-templating method. The structure of OSPN capsules can be precisely regulated by adjusting the molecular weight and concentration of PAMAM, thereby demonstrating a substantial impact on the kinetic behavior of the MIase@OSPN system. The MIase@OSPN system was used for catalytic production of mannose from D-fructose. A mannose yield of 22.24% was obtained, which is higher than that of MIase in organosilica network capsules and similar to that of the free enzyme. The overall catalytic efficiency (kcat/Km) of the MIase@OSPN system for the substrate D-fructose was up to 0.556 s−1·mmol−1·L. Meanwhile, the MIase@OSPN system showed excellent stability and recyclability, maintaining more than 50% of the yield even after 12 cycles.
The atom-economical cycloaddition of CO2 with epoxides to synthesize cyclic carbonates is a promising route for valuable utilization of CO2. Halogenide such as alkali metal halides and quaternary ammonium salt have been developed as the efficient catalysts. However, the spilled halogen causes equipment corrosion and affects the product purity. To address these concerns, the halogen-free cycloaddition of CO2 with epoxides has always been desired. In this review, we systematically discussed the halogen-free catalysis for cycloaddition of CO2 with epoxides from the mechanistic insights, aiming to promote the development of efficient halogen-free catalysts. Two types of catalysts, i.e., alternatives of halogen nucleophiles for epoxide activation, and bifunctional catalysts with Lewis acid-base sites for synergistic activation of CO2 and epoxides are summarized and emphasized. Specially, metal oxides as the potential halogen-free catalysts are highlighted due to their flexible acid-base sites for synergistic activation of CO2 and epoxides, facile preparation, and low cost.
Biomass-derived carbon materials for lithium-ion batteries emerge as one of the most promising anodes from sustainable perspective. However, improving the reversible capacity and cycling performance remains a long-standing challenge. By combining the benefits of K2CO3 activation and KMnO4 hydrothermal treatment, this work proposes a two-step activation method to load MnO2 charge transfer onto biomass-derived carbon (KAC@MnO2). Comprehensive analysis reveals that KAC@MnO2 has a micro-mesoporous coexistence structure and uniform surface distribution of MnO2, thus providing an improved electrochemical performance. Specifically, KAC@MnO2 exhibits an initial charge-discharge capacity of 847.3/1813.2 mAh·g–1 at 0.2 A·g–1, which is significantly higher than that of direct pyrolysis carbon and K2CO3 activated carbon, respectively. Furthermore, the KAC@MnO2 maintains a reversible capacity of 652.6 mAh·g–1 after 100 cycles. Even at a high current density of 1.0 A·g–1, KAC@MnO2 still exhibits excellent long-term cycling stability and maintains a stable reversible capacity of 306.7 mAh·g–1 after 500 cycles. Compared with reported biochar anode materials, the KAC@MnO2 prepared in this work shows superior reversible capacity and cycling performance. Additionally, the Li+ insertion and de-insertion mechanisms are verified by ex situ X-ray diffraction analysis during the charge-discharge process, helping us better understand the energy storage mechanism of KAC@MnO2.
Breakage of the C–N bond is a structure sensitive process, and the catalyst size significantly affects its activity. On the active metal nanoparticle scale, the role of catalyst size in C–N bond cleavage has not been clearly elucidated. So, Ru catalysts with variable nanoparticle sizes were obtained by modulating the reduction temperature, and the catalytic activity was evaluated using 1,2,3,4-tetrahydroquinoline and o-propylaniline with different C–N bond hybridization patterns as reactants. Results showed a 13 times higher reaction rate for sp3-hybridized C–N bond cleavage than sp2-hybridized C–N bond cleavage, while the reaction rate tended to increase first and then decrease as the catalyst nanoparticle size increased. Different concentrations of terrace, step, and corner sites were found in different sizes of Ru nanoparticles. The relationship between catalytic site variation and C–N bond cleavage activity was further investigated by calculating the turnover frequency values for each site. This analysis indicates that the variation of different sites on the catalyst is the intrinsic factor of the size dependence of C–N bond cleavage activity, and the step atoms are the active sites for the C–N bond cleavage. When Ru nanoparticles are smaller than 1.9 nm, they have a strong adsorption effect on the reactants, which will affect the catalytic performance of the Ru catalyst. Furthermore, these findings were also confirmed on other metallic Pd/Pt catalysts. The role of step sites in C–N bond cleavage was proposed using the density function theory calculations. The reactants have stronger adsorption energies on the step atoms, and step atoms have d-band center nearer to the Fermi level. In this case, the interaction with the reactant is stronger, which is beneficial for activating the C–N bond of the reactant.
The catalytic volcano activity models are the quantified and visualized tools of the Sabatier principle for heterogeneous catalysis, which can depict the intrinsic activity optima and trends of a catalytic reaction as a function of the reaction descriptors, i.e., the bonding strengths of key reaction species. These models can be derived by microkinetic modeling and/or free energy changes in combination with the scaling relations among the reaction intermediates. Herein, we introduce the CatMath—an online platform for generating a variety of common and industrially important thermal + electrocatalysis. With the CatMath, users can request the volcano models for available reactions and analyze their materials of interests as potential catalysts. Besides, the CatMath provides the function of the online generation of Surface Pourbaix Diagram for surface state analysis under electrocatalytic conditions, which is an essential step before analyzing the activity of an electrocatalytic surface. All the model generation and analysis processes are realized by cloud computing via a user-friendly interface.
NiFe2O4 is a kind of bimetallic oxide possessing excellent theoretical capacity and application prospect in the field of supercapacitors. Whereas, due to the inherent poor conductivity of metal oxides, the performance of NiFe2O4 is not ideal in practice. Oxygen vacancies can not only enhance the conductivities of NiFe2O4 but also provide better adsorption of OH, which is beneficial to the electrochemical performances. Hence, oxygen vacancies engineered NiFe2O4 (NiFe2O4‒δ) is obtained through a two-step method, including a hydrothermal reaction and a further heat treatment in activated carbon bed. Results of electron paramagnetic resonance spectra indicate that more oxygen vacancies exist in the treated NiFe2O4‒δ than the original one. UV-Vis diffuse reflectance spectra prove that the treated NiFe2O4‒δ owns better conductivity than the original NiFe2O4. As for the electrochemical performances, the treated NiFe2O4‒δ performs a high specific capacitance of 808.02 F∙g‒1 at 1 A∙g‒1. Moreover, the asymmetric supercapacitor of NiFe2O4‒δ//active carbon displays a high energy density of 17.7 Wh∙kg‒1 at the power density of 375 W∙kg‒1. This work gives an effective way to improve the conductivity of metal oxides, which is beneficial to the application of metal oxides in supercapacitors.
The increasing demand for potable water is never-ending. Freshwater resources are scarce and stress is accumulating on other alternatives. Therefore, new technologies and novel optimization methods are developed for the existing processes. Membrane-based processes are among the most efficient methods for water treatment. Yet, membranes suffer from severe operational problems, namely fouling and temperature polarization. These effects can harm the membrane’s permeability, permeate recovery, and lifetime. To mitigate such effects, membranes can be treated through two techniques: plasma treatment (a surface modification technique), and treatment through the use of plasmonic materials (surface and bulk modification). This article showcases plasma- and plasmonic-based treatments in the context of water desalination/purification. It aims to offer a comprehensive review of the current developments in membrane-based water treatment technologies along with suggested directions to enhance its overall efficiency through careful selection of material and system design. Moreover, basic guidelines and strategies are outlined on the different membrane modification techniques to evaluate its prerequisites. Besides, we discuss the challenges and future developments about these membrane modification methods.
The cycloaddition reaction between epoxides and CO2 is an effective method to utilize CO2 resource. Covalent organic frameworks (COFs) provide a promising platform for the catalytic CO2 transformations on account of their remarkable chemical and physical properties. Herein, a family of novel vinylene-linked ionic COFs named TE-COFs (TTE-COF, TME-COF, TPE-COF, TBE-COF) has been facilely synthesized from N-ethyl-2,4,6-trimethylpyridinium bromide and a series of triphenyl aromatic aldehydes involving different numbers of nitrogen atoms in the central aromatic ring. The resulting catalyst TTE-COF with excellent adsorption capacity (45.6 cm3·g–1, 273 K) exhibited outstanding catalytic performance, remarkable recyclability and great substrate tolerance. Moreover, it was also observed that the introduction of nitrogen atom in the precursor led to a great improvement in the crystallinity and CO2 adsorption capacity of TE-COFs, thus resulting to a progressively improved catalytic performance. This work not only illustrated the influence of monomer nitrogen content on the crystallinity and CO2 adsorption capacity of TE-COFs but also provided a green heterogeneous candidate for catalyzing the cycloaddition between CO2 and epoxides, which shed a light on improving the catalytic performance of the CO2 cycloaddition reaction by designing the covalent organic frameworks structures.
In this study, we synthesize a catalyst comprising cobalt nanoparticles supported on MXene by pyrolyzing a composite in a N2 environment. Specifically, the composite comprises a bimetallic Zn/Co zeolitic imidazole framework grown in situ on the outer surface of MXene. The catalytic efficiency of the catalyst is tested for the self-coupling of 4-methoxybenzylamine to produce value-added imine, where atmospheric oxygen (1 atm) is used as the oxidant. Based on the results, the catalyst displayed impressive catalytic activity, achieving 95.4% yield of the desired imine at 383 K for 8 h. Furthermore, the catalyst showed recyclability and tolerance toward benzylamine substrates with various functional groups. The outstanding performance of the catalyst is primarily attributed to the synergetic catalytic effect between the cobalt nanoparticles and MXene support, while also benefiting from the three-dimensional porous structure. Additionally, a preliminary investigation of potential reaction mechanisms is conducted.
The composition of biomass pyrolysis gas is complex, and the selective separation of its components is crucial for its further utilization. Metal-incorporated nitrogen-doped materials exhibit enormous potential, whereas the relevant adsorption mechanism is still unclear. Herein, 16 metal-incorporated nitrogen-doped carbon materials were designed based on the density functional theory calculation, and the adsorption mechanism of pyrolysis gas components H2, CO, CO2, CH4, and C2H6 was explored. The results indicate that metal-incorporated nitrogen-doped carbon materials generally have better adsorption effects on CO and CO2 than on H2, CH4, and C2H6. Transition metal Mo- and alkaline earth metal Mg- and Ca-incorporated nitrogen-doped carbon materials show the potential to separate CO and CO2. The mixed adsorption results of CO2 and CO further indicate that when the CO2 ratio is significantly higher than that of CO, the saturated adsorption of CO2 will precede that of CO. Overall, the three metal-incorporated nitrogen-doped carbon materials can selectively separate CO2, and the alkaline earth metal Mg-incorporated nitrogen-doped carbon material has the best performance. This study provides theoretical guidance for the design of carbon capture materials and lays the foundation for the efficient utilization of biomass pyrolysis gas.
The use of functional materials such as carbon-bismuth oxyhalides in integrated photorefineries for the clean production of fine chemicals requires restructuring. A facile biomass-assisted solvothermal fabrication of carbon/bismuth oxychloride nanocomposites (C/BiOCl) was achieved at various temperatures. Compared with BiOCl and C/BiOCl-120, C/BiOCl-180 exhibited higher crystallinity, wider visible light absorption, and a faster migration/separation rate of photoinduced carriers. For the selective C–C bond cleavage of biomass-based feedstocks photocatalyzed by C/BiOCl-180, the xylose conversion and lactic acid yield were 100% and 92.5%, respectively. C/BiOCl-180 efficiently converted different biomass-based monosaccharides to lactic acid, and the efficiency of pentoses was higher than that of hexoses. Moreover, lactic acid synthesis was favored by all active radicals including superoxide ion (·O2−), holes (h+), hydroxyl radical (·OH), and singlet oxygen (1O2), with ·O2− playing a key role. The fabricated photocatalyst was stable, economical, and recyclable. The use of biomass-derived monosaccharides for the clean production of lactic acid via the C/BiOCl-180 photocatalyst has opened new research horizons for the investigation and application of C–C bond cleavage in biomass-based feedstocks.
Foam trays with porous submerged orifices endow bubbles uniformly distributed, which are considered attractive column internals to enhance the gas-liquid mass transfer process. However, its irregular orifice and complex gas-liquid flow make it lack pore-scale investigations concerning the transfer mechanism of dynamic bubbling. In this work, the actual porous structure of the foam tray is obtained based on micro computed tomography technology. The shape, dynamic, and mass transfer of rising bubbles at porous orifices are investigated using the volume of fluid and continue surface force model. The results demonstrate that the liquid encroaching on the gas channels causes the increasing orifices velocity, which makes the trailing bubble easily detach from the midst of the leading bubble and causes pairing coalescence. Additionally, we found that the central breakup regimes significantly improve the gas-liquid interface area and mass transfer efficiency. This discovery exemplifies the mechanism of mass transfer intensification for foam trays and serves to promote its further development.
Continuous glucose monitoring (CGM) systems play an increasingly vital role in the glycemic control of patients with diabetes mellitus. However, the immune responses triggered by the implantation of poorly biocompatible sensors have a significant impact on the accuracy and lifetime of CGM systems. In this review, research efforts over the past few years to mitigate the immune responses by enhancing the anti-biofouling ability of sensors are summarized. This review divided these works into active immune engaging strategy and passive immune escape strategy based on their respective mechanisms. In each strategy, the various biocompatible layers on the biosensor surface, such as drug-releasing membranes, hydrogels, hydrophilic membranes, anti-biofouling membranes based on zwitterionic polymers, and bio-mimicking membranes, are described in detail. This review, therefore, provides researchers working on implantable biosensors for CGM systems with vital information, which is likely to aid in the research and development of novel CGM systems with profound anti-biofouling properties.
Metal-organic framework/organosilica hybrid membranes on tubular ceramic substrates have shown great potential for the implementation of membrane technology in practical gas separation projects due to their higher permeance compared to commercial polymers. However, the selectivities of the reported membranes are moderate. Here, we have incorporated urea-modulated metal-organic frameworks into organosilica membranes to greatly enhance its separation performance. The urea-modulated metal-organic frameworks exhibit less-defined edges of crystallographic facets and high defect density. They can be well-dispersed in the organosilica layer, which substantially suppresses the interfacial defects between metal-organic frameworks and organosilica, which is beneficial for improving the selectivity of membranes for gas separation. The results have shown that the enhanced ideal selectivity of H2/CH4 was 165 and that of CO2/CH4 was 43, with H2 permeance of about 1.25 × 10−6 mol·m−2·s−1·Pa−1 and CO2 permeance of 3.27 × 10−7 mol·m−2·s−1·Pa−1 at 0.2 MPa and 25 °C. In conclusion, the high level of hybrid membranes can be used to separate H2 (or CO2) from the binary gas mixture H2/CH4 (or CO2/CH4), which is important for gas separation in practical applications. Moreover, the simple and feasible modulation of metal-organic framework is a promising strategy to tune different metal-organic frameworks for membranes according to the actual demands.
Membrane gas separation is considered an energy-saving technique to extract He from natural gas due to no phase change and room temperature operation. However, the membrane performance was strongly limited by the trade-off between permeance and selectivity. Herein, novel 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-2,2′-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (APAF)-5-amino-2-(4-aminobenzene)benzimidazole (BIA) asymmetric membranes with a thickness of 300 nm were successfully prepared by the non-solvent induced phase separation method. The membrane performance was modulated by regulating dope solution compositions (e.g., tetrahydrofuran and polymer concentration). The ideal He/CH4 selectivity was 124 and the optimized He permeance reached 87 GPU, beyond the current upper bound. He/CH4 selectivity was 75 and He permeance was 73 GPU for the binary mixture feed containing 0.2 mol % He. The membrane showed good resistance to CO2 and C2H6, which are the typical impurities in natural gas. The 6FDA-APAF-BIA membranes have good stability (> 160 h), which can provide great potential in He extraction from natural gas.
This study utilized a thermogravimetric analyzer to assess the thermal decomposition behaviors and kinetics properties of vacuum residue (VR) and low-density polyethylene (LDPE) polymers. The kinetic parameters were calculated using the Friedman technique. To demonstrate the interactive effects between LDPE and VR during the co-pyrolysis process, the disparity in mass loss and mass loss rate between the experimental and calculated values was computed. The co-pyrolysis curves obtained through estimation and experimentation exhibited significant deviations, which were influenced by temperature and mixing ratio. A negative synergistic interaction was observed between LDPE and VR, although this inhibitory effect could be mitigated or eliminated by reducing the LDPE ratio in the mixture and increasing the co-pyrolysis temperature. The co-pyrolysis process resulted in a reduction in carbon residue, which could be attributed to the interaction between LDPE and the heavy fractions, particularly resin and asphaltene, present in VR. These findings align with the pyrolysis behaviors exhibited by the four VR fractions. Furthermore, it was observed that the co-pyrolysis process exhibited lower activation energy as the VR ratio increased, indicating a continuous enhancement in the reactivity of the mixed samples during co-pyrolysis.
In a dual-chamber photocatalytic fuel cell device, polyvinyl alcohol degradation and H2 evolution were concurrently achieved. The setup involved commercial P25 as the photoanode and Ag@Fe2O3 nanoparticles as the cathode. Additionally, the feasibility of a Fenton-like reaction in the cathode, utilizing Fe2+ ions and pumped O2, was demonstrated. Different cathode materials, polyvinyl alcohol types, and pH values’ effects were assessed on device performance. Quenching tests highlighted photoinduced holes (h+) and OH· radicals as pivotal contributions to polyvinyl alcohol degradation. Long-term stability of the device was established through cycling experiments.
During steam reforming, the performance of a catalyst and amount/property of coke are closely related to reaction intermediates reaching surface of a catalyst. Herein, modification of reaction intermediates by placing Mg-Al-hydrotalcite above Ni/KIT-6 catalyst in steam reforming of glycerol was conducted at 300 to 600 °C. The results revealed that the catalytic activity of Ni/KIT-6 in the lower bed was enhanced with either Mg1-Al5-hydrotalcite (containing more acidic sites) or Mg5-Al1-hydrotalcite (containing more alkaline sites) as upper-layer catalyst. The in situ infrared characterization of steam reforming demonstrated that Mg-Al-hydrotalcite catalyzed the deoxygenation of glycerol, facilitating the reforming of the partially deoxygenated intermediates over Ni/KIT-6. Mg-Al-hydrotalcite as protective catalyst, however, did not protect the Ni/KIT-6 from formation of more coke. Nonetheless, this did not lead to further deactivation of Ni/KIT-6 while Mg5-Al1-hydrotalcite even substantially enhanced the catalytic stability, even though the coke was much more significant than that in the use of single Ni/KIT-6 (52.7% vs. 28.6%). The reason beneath this was change of the property of coke from more aliphatic to more aromatic. Mg5-Al1-hydrotalcite catalyzed dehydration of glycerol, producing dominantly reaction intermediates bearing C=C, which formed the catalytic coke of with carbon nanotube as the main form with smooth outer walls as well as higher aromaticity, C/H ratio, crystallinity, crystal carbon size, thermal stability, and resistivity toward oxidation on Ni/KIT-6 in the lower bed. In comparison, the abundance of acidic sites on Mg1-Al5-hydrotalcite catalyzed the formation of more oxygen-containing species, leading to the formation of carbon nanotubes of rough surface on Ni/KIT-6.
Heteroatom doping and defect engineering have been proposed as effective ways to modulate the energy band structure and improve the photocatalytic activity of g-C3N4. In this work, ultrathin defective g-C3N4 was successfully prepared using cold plasma. Plasma exfoliation reduces the thickness of g-C3N4 from 10 nm to 3 nm, while simultaneously introducing a large number of nitrogen defects and oxygen atoms into g-C3N4. The amount of doped O was regulated by varying the time and power of the plasma treatment. Due to N vacancies, O atoms formed strong bonds with C atoms, resulting in O doping in g-C3N4. The mechanism of plasma treatment involves oxygen etching and gas expansion. Photocatalytic experiments demonstrated that appropriate amount of O doping improved the photocatalytic degradation of rhodamine B compared with pure g-C3N4. The introduction of O optimized the energy band structure and photoelectric properties of g-C3N4. Active species trapping experiments revealed ·O2– as the main active species during the degradation.