Dual-template synthesis of SFO-type aluminophosphate with enhanced water-sorption-driven cooling performance.

Water-based adsorption chillers (ADC) driven by low-grade thermal energy are environment-friendly alternatives to the traditional compression ones to realize the net zero carbon target. Aluminophosphates molecular sieve (AlPOs) is an excellent material for water-based adsorption applications. However, AlPOs suffers from relatively high cost attributed to the extensive use of expensive structure direct agents (SDAs). This study employed a dual-template method, using cheap organic amine as a dual-template, to synthesize low-cost and excellent adsorbent AlPOs with SFO topology (AlPO-SFO). AlPO-SFO synthesized with dual templates shows high crystallinity, large micropore volume, excellent water uptake, and low regeneration temperature. AlPO-SFO guided by 4-dimethylaminopyridine (4-DMAPy) and diethanolamine (DEOA) molar composition of 0.4 and 0.1 exhibits large microporous volume (0.30 ml g-1), high water uptake (0.26 g g-1 at P/P0 = 0.25) and low regeneration temperature (65 °C). Importantly, this AlPO-SFO exhibits a high coefficient of performance (COP) of 0.89 for cooling at a low driven temperature of 64 °C. The additive amine providing alkaline medium ensures the practical synthesis of AlPO-SFO when expensive 4-DMAPy decreases, endowing the 42 % reduction of the raw material cost. The results provide a cheaper synthesis route of AlPO-SFO, which is conducive to its large-scale production as a distinguished adsorbent for adsorption chillers.

Characterization of Water Vapor Sorption Performance and Heat Storage of MIL-101 (Cr) Complex MgCl2, LiCl/LaCl3 System for Adsorptive Thermal Conversion.

Adsorption heat conversion systems can provide heating and cooling across time and space in a more environmentally friendly way. Porous materials are potential candidates for water-based adsorption thermal conversion, in which a metal-organic framework (MOF) has a larger specific surface area and porosity than other porous matrices. However, many MOFs with high saturated adsorption capacity have great deficiencies in performance at low water vapor partial pressure, which hinder their application in adsorption thermal conversion. To improve the water vapor adsorption performance of MIL-101 (Cr), different contents of magnesium chloride, lithium chloride, and lanthanum chloride are mixed into MIL-101 (Cr) by an impregnation method. The properties and structures of the materials are characterized by XRD, SEM, nitrogen adsorption tests, water vapor adsorption tests, TG, FTIR, and so on. The results show that the saturated water vapor adsorption capacity of the sample impregnated with salt increases by 1.5-2.3 times, up to 2.24 g/g, compared with that of the unimpregnated sample. When the partial pressure of water vapor is 0.3, the adsorption capacity increases by 5.3-7.5 times and reaches 0.68 g/g at most. The maximum heat storage density of impregnated samples can be increased by 866 J/g. Impregnated MgCl2 can greatly improve the adsorption and thermal conversion performance of MOF, and impregnated MgCl2 and the proper amount of LiCl can further improve the performance of the material system. Our experiments show that the composite impregnation of magnesium chloride and the proper amount of lithium chloride can improve the application performance of the MOF materials in the adsorption thermal conversion process.

Improvement of water adsorption performance of UiO-66 by post-synthetic modification.

Post-synthetic modification can be used for structural replacement or functional modification of materials after they have been formed or assembled. It can effectively combine various modification methods for metal-organic frameworks (MOFs) such as defect control, replacement of metal sites, or functionalization of ligands. In this work, organic ligands that incorporate N-functionalities or amino groups were introduced into defective UiO-66 through post-synthetic ligand exchange (PSE) to improve its water adsorption performance. Parameters such as water adsorption capacity, half adsorption value (α), and Henry constant KH were used to characterize the water adsorption performance. After PSE, new ligands in different molar ratios entered the skeleton of UiO-66. The N sites or amino groups on the ligands provided new sites for the adsorption of water molecules. The water adsorption capacity and hydrophilicity of all samples were significantly superior to those of LD-UiO-66, which had almost no defects. H-UiO-66-PyDC samples exhibited the highest ligand replacement ratio and a significant enhancement of water adsorption performance. Compared to the unchanged H-UiO-66, the water uptake of H-UiO-66-PyDC increased from 0.08 g g-1 to 0.23 g g-1 at P/P0 = 0.30 and α decreased from 0.36 to 0.28. After 20 water adsorption/desorption tests, the water uptake of all samples did not decrease, showing excellent cycling stability. These results suggest that the combination of defect modulation and PSE is a potential tool to make UiO-66 more appropriate for applications based on reversible adsorption.

Dopamine-Mediated Graphene Bridging Hexagonal Boron Nitride for Large-Scale Composite Films with Enhanced Thermal Conductivity and Electrical Insulation.

Heat accumulation generated from confined space poses a threat to the service reliability and lifetime of electronic devices. To quickly remove the excess heat from the hot spot, it is highly desirable to enhance the heat dissipation in a specific direction. Herein, we report a facile route to fabricate the large-scale composite film with enhanced thermal conductivity and electrical insulation. The well-stacked composite films were constructed by the assembly of polydopamine (PDA)-modified graphene nanosheets (GNSPDA) and hexagonal boron nitride (BNPDA), as well as bacterial cellulose (BC). The introduction of the PDA layer greatly improves the interface compatibility between hybrid fillers and BC matrix, and the presence of GNSPDA-bridging significantly increases the probability of effective contact with BNPDA fillers, which is beneficial to form a denser and complete "BN-GNS-BN" heat conduction pathway and tight filler-matrix network, as supported by the Foygel model fitting and numerical simulation. The resulting BC/BNPDA/GNSPDA film shows the thermal conductivity and tensile strength of 34.9 W·m-1·K-1 and 30.9 MPa, which separately increases to 161% and 155% relative to the BC/BNPDA film. It was found that the low electrically conductive and high thermal conductive properties can be well balanced by tuning the mass ratio of GNSPDA at 5 wt%, and the electrical conductivity caused by GNSPDA can be effectively blocked by the BNPDA filler network, giving the low electrical conductivity of 1.8 × 10-10 S·cm-1. Meanwhile, the BC/BNPDA/GNSPDA composite films effectively transfer the heat and diminish the hot-spot temperature in cooling LED chip module application. Thus, the present study may pave the way to promoting the industrialization of scalable thermal management devices.

Maximizing Electric Power through Spectral-Splitting Photovoltaic-Thermoelectric Hybrid System Integrated with Radiative Cooling.

As zero-emission technologies, a daytime radiative cooling (RC) strategy developed recently, and photovoltaic (PV) and thermoelectric (TE) technologies have aroused great interest to reduce fossil fuel consumption and carbon emissions. How to integrate these state-of-the-art technologies to maximise clean electricity from the sun and space remains a huge challenge, and the limit efficiency is still unclear. In this study, a spectral-splitting PV-TE hybrid system integrated with RC is proposed to maximise clean electricity from the sun and space without any emissions. For the sun acting as a typical constant heat-flux heat source, the current thermoelectric theory overestimates the thermoelectric efficiency highly since the theory is based on constant temperature-difference conditions. A new theory based on heat-flux conditions is employed to achieve maximum thermoelectric efficiency. The PV-TE hybrid system with RC is superior to the conventional hybrid system, not only in terms of higher efficiency but also in its 24-h operation capacity. In a system with a single-junction cell, the total efficiency with 30 suns (39.4%) is higher than the theoretical PV efficiency at 500 suns (38.2%). In a hybrid system with four-junction cells, total efficiency is over 65% which is superior to most current photoelectric and thermal power systems.

Enhanced Water Adsorption Performance of UiO-66 Modulated with p-Nitrobenzoic or p-Hydroxybenzoic Acid: Introduced Defects and Functional Groups.

Adding appropriate modulators can effectively improve the porosity and adsorption performance of UiO-66. Herein, UiO-66 samples were synthesized with p-nitrobenzoic acid (PNBA) and p-hydroxybenzoic acid (PHBA) as modulators. All samples exhibited good crystallinity and thermal stability. The polar functional groups (-NO2 and -OH) and defects were introduced into UiO-66, which significantly improved its water adsorption performance and applications in adsorption heat transformation. With the addition of six equiv PNBA, the saturated water uptake of UiO-66 increased from 0.40 to 0.58 g/g. Also, 4eqPNBA-UiO-66 exhibited the highest water uptake under low relative pressure, which was almost twice that of "low-defect" LD-UiO-66. The addition of PHBA had little effect on the saturated water absorption. However, its highest water uptake at P/P0 = 0.3 is 0.23 g/g, which is equivalent to that of 4eqPNBA-UiO-66. Ten consecutive adsorption/desorption cycles indicated that these samples had good cycle stability.

Ultralow-temperature-driven water-based sorption refrigeration enabled by low-cost zeolite-like porous aluminophosphate.

Thermally driven water-based sorption refrigeration is considered a promising strategy to realize near-zero-carbon cooling applications by addressing the urgent global climate challenge caused by conventional chlorofluorocarbon (CFC) refrigerants. However, developing cost-effective and high-performance water-sorption porous materials driven by low-temperature thermal energy is still a significant challenge. Here, we propose a zeolite-like aluminophosphate with SFO topology (EMM-8) for water-sorption-driven refrigeration. The EMM-8 is characterized by 12-membered ring channels with large accessible pore volume and exhibits high water uptake of 0.28 g·g-1 at P/P0 = 0.2, low-temperature regeneration of 65 °C, fast adsorption kinetics, remarkable hydrothermal stability, and scalable fabrication. Importantly, the water-sorption-based chiller with EMM-8 shows the potential of achieving a record coefficient of performance (COP) of 0.85 at an ultralow-driven temperature of 63 °C. The working performance makes EMM-8 a practical alternative to realize high-efficient ultra-low-temperature-driven refrigeration.

A Comparative Study of Cavitation Characteristics of Nano-fluid and Deionized Water in Micro-channels.

Hydrodynamic cavitation has been widely applied in micro-fluidic systems. Cavitating flow characteristics are closely related to the fluid properties. In this paper, the cavitation characteristics of Cu nano-fluid in micro-channels were numerically investigated and compared with those of the deionized (DI) water. The mathematical model was verified by comparing the numerical results with the experiment observation. The curved orifice (R = 0.3 mm) was found to have the highest efficiencies of cavitation for both fluids. With the increase of inlet pressure, cavitating jet lengths of the two fluids significantly increased. While, the cavitating jet length of the nano-fluid was shorter than that of the DI water at the same inlet pressure. The cavitation inception number of the DI water and nano-fluid were approximately 0.061 and 0.039, respectively. The results indicate that the nano-particles played negative effects on the cavitation inception. In addition, with the decrease of outlet pressure, the cavitation strength gradually increased and the mass flow rate remained nearly unchanged at the same time.

Screening of metal-organic frameworks for water adsorption heat transformation using structure-property relationships.

It is of great importance to correlate the water adsorption performance of MOFs to their physicochemical features in order to design and prepare MOFs for applications in adsorption heat transformation. In this work, both data analysis from existing studies and Grand Canonical Monte Carlo molecular simulation investigations were carried out. The results indicated that the highest water adsorption capacity was determined by the pore volume of MOF adsorbents, while there was a linear correlation interrelationship between isosteric heats of adsorption and the water adsorption performance at a low relative pressure. More detailed analysis showed that the charge distribution framework and pore size of MOFs contributed together to the hydrophilicity. Electrostatic interaction between water molecules and the framework atoms played a key role at low relative water pressure. A quantitative structure-property relationship model that can correlate the hydrophilicity of MOFs to their pore size and atomic partial charge was established. Along with some qualitative considerations, the screening methodology is proposed and is used to screen proper MOFs in the CoRE database. Seven MOFs were detected, and four of them were synthesized to validate the screening principle. The results indicated that these four MOFs possessed outstanding water adsorption performance and could be considered as promising candidates in applications for adsorption heating and cooling.

Enhanced thermal conductance at the graphene-water interface based on functionalized alkane chains.

Highly efficient thermal transport between graphene and water is crucial in applications such as microscopic heat dissipation, solar steam generation, sea-water desalination, and thermally conductive composites. However, a practical approach for enhancing thermal transport across graphene-water interfaces is lacking. We propose an effective and universal method to improve thermal-transport properties at the interface between multilayer graphene and water by a factor of ∼4 by grafting functionalized groups onto graphene. The most improved interfacial thermal conductance was 121.0 ± 11.4 MW m-2 K-1. This design is compatible with industrial processes. We also undertook molecular-level analyses to unveil the underlying mechanism for heat-transport enhancement. This study could provide new approaches for engineering heat transport across two-dimensional materials and water interfaces.

Correction: Enhanced thermal conductance at the graphene-water interface based on functionalized alkane chains.

[This corrects the article DOI: 10.1039/C8RA09879D.].

A novel antibiotic wastewater degradation technique combining cavitating jets impingement with multiple synergetic methods.

Antibiotics degradation remains a longstanding challenge in wastewater treatment. Towards this objective, we have developed a novel technique combining cavitating jets impingement with multiple synergetic methods, i.e., UV/Fenton, analogous Fenton, and photocatalytic oxidation in the present work. Three kinds of antibiotics namely amoxicillin, doxycycline and sulfadiazine sodium, are selected as model pollutants. Individual application of cavitating jets impingement is firstly conducted to evaluate the effects of jets impinging forms and nozzle inlet pressure. The effects of impingement on promoting antibiotics degradation and weakening the coalescing effects of cavitation bubbles are confirmed. Perpendicular double cavitating jets impingement is proved to be the most effective impinging form and brought a COD (chemical oxidation demand) reduction of 30.04% with the impinging effect index 1.22 at jet inlet pressure 10 MPa. Increasing the jet inlet pressure can improve the COD reduction and the effectiveness of impingement. Subsequently, UV/Fenton process is introduced to intensify the degradation process. The effects of important parameters are investigated by means of orthogonal experiments and the maximum COD reduction is up to 71.16% under the optimum conditions. Then, analogous Fenton process and photocatalytic oxidation are adopted for further enhancing the COD reduction. Different approaches used in the present work are assessed in view of multiple aspects. With COD reduction of 79.92%, the combination of cavitating jets impingement, UV/Fenton, analogous Fenton and photocatalytic oxidation is proved to be optimum method for antibiotic wastewater treatment.

A novel device for hazardous substances degradation based on double-cavitating-jets impingement: Parameters optimization and efficiency assessment.

Hydrodynamic cavitation is an effective advanced oxidation process. But sometimes it cannot obtain satisfactory treatment efficiency by using hydrodynamic cavitation individually, so it is necessary to introduce intensive methods. Based on double-cavitating-jets impingement, this paper presents a novel device that has advantages of strong heat and mass transfer and efficient chemical reactions. Based on the device, a series of experimental investigations on degradation of a basic dye, i.e. Rhodamine B were carried out. Significant Rhodamine B removal from aqueous solution was observed during 2h treatment and the degradation reaction conformed to pseudo-first-order kinetics. The synergetic effects between double-cavitating-jets impingement and Fenton chemistry on simultaneous degradation of Rhodamine B were confirmed. Both single-variable experiments and orthogonal experiments were carried out to study the effects of initial hydrogen peroxide, ferrous sulfate and Rhodamine B concentrations and the optimum conditions were found out. Effects of jet inlet pressure in the range of 6-12MPa and solution pH value in the range of 2-8 were also investigated. The cavitation yield was evaluated to assess the energy efficiency. The present treatment scheme showed advantages in terms of reducing the demand of hydrogen peroxide concentration and enhancing the treatment efficiency in large scale operation.

Ultrasound promoted catalytic liquid-phase dehydrogenation of isopropanol for Isopropanol-Acetone-Hydrogen chemical heat pump.

The apparent kinetic of the ultrasound assisted liquid-phase dehydrogenation of isopropanol over Raney nickel catalyst was determined in the temperature range of 346-353 K. Comparison of the effects of ultrasound and mechanical agitation on the isopropanol dehydrogenation was investigated. The ultrasound assisted dehydrogenation rate was significantly improved when relatively high power density was used. Moreover, the Isopropanol-Acetone-Hydrogen chemical heat pump (IAH-CHP) with ultrasound irradiation, in which the endothermic reaction is exposure to ultrasound, was proposed. A mathematical model was established to evaluate its energy performance in term of the coefficient of performance (COP) and the exergy efficiency, into which the apparent kinetic obtained in this work was incorporated. The operating performances between IAH-CHP with ultrasound and mechanical agitation were compared. The results indicated that the superiority of the IAH-CHP system with ultrasound was present even if more than 50% of the power of the ultrasound equipment was lost.

Influence of longitudinal rise of coolant temperature on the thermal strain in a cylindrical laser rod.

The thermal strain in a laser rod with a longitudinal temperature increase is modeled and analytically derived through the method of thermoelastic displacement potential and the method of Love displacement function. The analytical results show that in the absence of external forces, the longitudinal rise of fluid temperature has an unnoticeable effect on the thermal stress profile in the laser rod. However, the thermal strain field caused by the temperature distribution under the traction free boundary condition has an evident variation in the longitudinal direction, which will considerably affect the laser transmission characteristics and the beam quality.

Analysis of thermal effects in an orthotropic laser medium.

The temperature, thermal stress, thermal strain, and optical path difference (OPD) in an orthotropic laser medium under Gaussian, top-hat, and uniform pumping schemes are solved both analytically and numerically. The results indicate that, provided the same total heat loading, the thermal effects under the top-hat pumping scheme are lower than under the Gaussian pumping scheme, whereas the thermal effects under uniform pumping are the least significant of all; in the absence of external forces, the orthotropic thermal properties have more significant effects on the thermal strain than on the thermal stress. The theoretical OPD agrees well with published experimental data and shows evident orthotropy.