Current trends in structural development and modification strategies for metal-organic frameworks (MOFs) towards photocatalytic H2 production: A review

Photocatalytic H₂ generation using semiconductor photocatalysts is considered as a cost-effective and eco-friendly technology for solar to energy conversion; however, the present photocatalysts have been recognized to depict low efficiency. Currently, porous coordination polymers known as metal-organic frameworks (MOFs) constituting flexible and modifiable porous structure and having excess active sites are considered to be appropriate for photocatalytic H₂ production. This review highlights current progress in structural development of MOF materials along with modification strategies for enhanced photoactivity. Initially, the review discusses the photocatalytic H₂ production mechanism with the concepts of thermodynamics and mass transfer with particular focus on MOFs. Elaboration of the structural categories of MOFs into Type I, Type II, Type III and classification of MOFs for H₂ generation into transition metal based, post-transition metal based, noble-metal based and hetero-metal based has been systematically discussed. The review also critically deliberate various modification approaches of band engineering, improvement of charge separation, efficient irradiation utilization and overall efficiency of MOFs including metal modification, heterojunction formation, Z-scheme formation, by introducing electron mediator, and dye based composites. Also, the MOF synthesized derivatives for photocatalytic H₂ generation are elaborated. Finally, future perspectives of MOFs for H₂ generation and approaches for efficiency improvement have been suggested.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Effect of plasma treatment of polymeric tape carriers on wetting behaviour of aqueous ceramic tape casting slurry

Due to environmental and health aspects, aqueous ceramic slurries are preferred to traditional organic solvent systems in tape casting. An important obstacle associated with the high surface energy of water is poor wetting of aqueous ceramic slurries on polymeric tape carriers. Therefore, we measured the contact angles of an aqueous epoxy-based ceramic slurry on polyethylene terephtalate (PET), polypropylene (PP), polymethyl methacrylate (PMMA), and aluminium-coated polyethylene terephtalate (PET-Al) films and investigated approaches to improving their wetting. We evaluated the effect of plasma treatment of the tape carrier surface on the wetting behaviour and compared it with the effect of adding non-ionic amphiphilic surfactants to the ceramic slurry. The treatment of the tape carrier surface by low-temperature plasma substantially improved the wetting behaviour of aqueous ceramic slurry. The lowest contact angle of 31° was obtained on the PET film. Although the addition of non-ionic surfactants improved both the wetting behaviour of the slurry and the detachment of the polymeric carrier from the ceramic tape even better than the plasma treatment of the carrier surface did, the plasma-treated carriers still present a useful alternative to the surfactants. In the case of the plasma-treated PET carrier the surfactants could be fully eliminated and potential drawbacks related to the use of surfactants could be prevented.     

Adsorptive removal of methylene blue from aqueous solution on activated carbon prepared from Malawian baobab fruit shell wastes: Equilibrium,kinetics and thermodynamic studies

Baobab fruit shell (BFS), a renewable bio-waste from Malawian baobab tree was used as a precursor for the production of a low-cost activated carbon to remove methylene blue (MB) from aqueous solution. Parameters such as contact time, initial methylene blue concentration, adsorbent dose and temperature were studied. The adsorption process can be well described by both Langmuir isotherm and the pseudo-second-order kinetics. The maximum monolayer adsorption capacity of MB dye was ca. 334.45 mg/g. The negative value of the Gibb’s free energy and positive value of adsorption enthalpy showed the spontaneous nature and endothermic nature of the adsorption process, respectively.     

Advances in statistical mechanics of rock masses and its engineering applications

To efficiently link the continuum mechanics for rocks with the structural statistics of rock masses,a theoretical and methodological system called the statistical mechanics of rock masses(SMRM)was developed in the past three decades.In SMRM,equivalent continuum models of stressestrain relationship,strength and failure probability for jointed rock masses were established,which were based on the geometric probability models characterising the rock mass structure.This follows the statistical physics,the continuum mechanics,the fracture mechanics and the weakest link hypothesis.A general constitutive model and complete stressestrain models under compressive and shear conditions were also developed as the derivatives of the SMRM theory.An SMRM calculation system was then developed to provide fast and precise solutions for parameter estimations of rock masses,such as full-direction rock quality designation(RQD),elastic modulus,Coulomb compressive strength,rock mass quality rating,and Poisson’s ratio and shear strength.The constitutive equations involved in SMRM were integrated into a FLAC3D based numerical module to apply for engineering rock masses.It is also capable of analysing the complete deformation of rock masses and active reinforcement of engineering rock masses.Examples of engineering applications of SMRM were presented,including a rock mass at QBT hydropower station in northwestern China,a dam slope of Zongo II hydropower station in D.R.Congo,an open-pit mine in Dexing,China,an underground powerhouse of Jinping I hydropower station in southwestern China,and a typical circular tunnel in Lanzhou-Chongqing railway,China.These applications verified the reliability of the SMRM and demonstrated its applicability to broad engineering issues associated with jointed rock masses.     

Influence of soil density on gas permeability and water retention in soils amended with in-house produced biochar

Biochar has been used as an environment-friendly enhancer to improve the hydraulic properties(e.g.suction and water retention) of soil.However,variations in densities alter the properties of the soil-biochar mix.Such density variations are observed in agriculture(loosely compacted) and engineering(densely compacted) applications.The influence of biochar amendment on gas permeability of soil has been barely investigated,especially for soil with diffe rent densities.The maj or obj ective of this study is to investigate the water retention capacity,and gas permeability of biochar-amended soil(BAS) with different biochar contents under varying degree of compaction(DOC) conditions.In-house produced novel biochar was mixed with the soil at different amendment rates(i.e.biochar contents of 0%,5% and 10%).All BAS samples were compacted at three DOCs(65%,80% and 95%) in polyvinyl chloride(PVC)tubes.Each soil column was subjected to drying-wetting cycles,during which soil suction,water content,and gas permeability were measured.A simplified theoretical framework for estimating the void ratio of BAS was proposed.The experimental results reveal that the addition of biochar significantly decreased gas permeability k_g as compared with that of bare soil(BS).However,the addition of 5%biochar is found to be optimum in decreasing kg with an increase of DOC(i.e.k_(g,65%) k_(g,80%) k_(g,95%)) at a relatively low suction range(200 kPa) because both biochar and compaction treatment reduce the connected pores.     

Investigation on sulphonated zinc oxide nanorod incorporated sulphonated poly (1,4-phenylene ether ether sulfone) nanocomposite membranes for improved performance of microbial fuel cell

Hydrothermally prepared zinc oxide nanorods are sulphonated (S–ZnO NR) and incorporated into 15% Sulphonated Poly (1,4-Phenylene Ether Ether Sulfone) (SPEES) to improve the hydrophilicity, water uptake and ion transfer capacity. Water uptake and ion transfer capacity increased to 34.6 ± 0.6% and 2.0 ± 0.05 meq g^?1 from 29.8 ± 0.3% and 1.4 ± 0.04 meq g^?1 by adding 7.5 wt% S–ZnO NR to SPEES. Morphological studies show the prepared S–ZnO NR is well dispersed in the polymer matrix. SPEES +7.5 wt% S–ZnO NR membrane exhibits optimum performance after three-weeks of continual operation in a fabricated microbial fuel cell (MFC) to produce a maximum power density of 142 ± 1.2 mW m^?2 with a reduced biofilm compared to plain SPEES (59 ± 0.8 mW m^?2), unsulphonated filler incorporated SPEES (SPEES + 7.5 wt% ZnO, 68 ± 1.1 mW m^?2) and Nafion (130 ± 1.5 mW m^?2) thereby suggesting its suitability as a sustainable and improved cation exchange membrane (CEM) for MFCs.     

苯乳酸抑制链格孢霉作用靶位的分析

以从自然腐败的樱桃上分离的链格孢霉（Alternaria sp.）LD3.0086为指示菌，研究苯乳酸对链格孢霉的主要抑制作用靶位。应用分光光度法测定苯乳酸对链格孢霉的最小抑菌浓度，通过卡尔科弗卢尔荧光增白剂染液（calcofluor white，CFW）染色观察苯乳酸对菌丝顶端生长的破坏作用，利用扫描电子显微镜和透射电子显微镜观察链格孢霉的超微结构变化，通过测定苯乳酸作用前后链格孢霉上清液中N-乙酰葡萄糖胺质量浓度变化研究苯乳酸对菌丝细胞壁的破坏作用，应用荧光双染色法观察苯乳酸对链格孢霉菌丝细胞膜的损伤作用。结果表明，12.5 mmol/L的苯乳酸能有效抑制链格孢霉的生长；与对照组（无菌水处理）相比，苯乳酸处理后链格孢霉顶端生长细胞无明显形变，经12.5 mmol/L苯乳酸处理的链格孢霉上清液中N-乙酰葡萄糖胺质量浓度基本不变；苯乳酸处理24 h，链格孢霉菌丝细胞壁表面无明显损伤，细胞内结构发生明显变化；苯乳酸短时间（4 h）处理链格孢霉，菌丝细胞膜仍较为完整，加入苯乳酸较长时间（8 h）后细胞膜发生破裂。综合分析可知，苯乳酸对链格孢霉的主要作用靶位应不是菌丝体的细胞壁和细胞膜，而是在菌丝体内部，通过破坏菌丝内部细胞器结构或引起细胞内的生化反应，从而抑制链格孢霉的生长和繁殖，发挥抑菌活性。     

Design and construction of lightweight EPS geofoam embedded geomaterial embankment system for control of settlements

This paper presents a research study on a bridge site located along US highway 67 over SH 174 in Cleburne, Texas, where bridge approach slabs have experienced more than 0.4 m (17 in.) of settlement within a span of 16 years after construction. Many treatment methods attempted to mitigate this problem had proven to be ineffective. As part of novel rehabilitation works, the top of existing fill soil on the embankment was replaced with lightweight expanded polystyrene (EPS) geofoam blocks to alleviate the approach slab settlements. This paper describes initial design and construction details of the rehabilitation works performed on the embankment system along with a focus on the early performance details. Field monitoring studies were conducted for almost three years to study the bump/settlements under the EPS geofoam embankment system. Short term measured settlement data was analyzed with hyperbolic model to predict the long term settlements. Numerical finite element studies attempted in this study showed that settlements could be reasonably predicted by modeling these geofoam embankments. Based on the monitoring and modeling studies, the effectiveness of utilizing EPS geofoam as an embankment fill material was addressed to mitigate the differential settlements under a bridge approach slab.