Surface reconstruction,modification and functionalization of natural diatomites for miniaturization of shaped heterogeneous catalysts

Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there have also been considerable interests in endowing them with hierarchical porosities to overcome the diffusional limitation for those with long unimodal channels.Present processes of making mesoporous silica largely rely on chemical sources which are relatively expensive and impose environmental concerns on their processes.In this regard,it is desirable to develop hierarchical silica supports from natural minerals.Herein,we present a series of work on surface reconstruction,modification,and functionalization to produce diatomite-based catalysts with original morphology and macro-meso-micro porosities and to test their suitability as catalyst supports for both liquid-and gas-phase reactions.Two wet-chemical routes were developed to introduce mesoporosity to both amorphous and crystalline diatomites.Importantly,we have used computational modeling to affirm that the diatomite morphology can improve catalytic performance based on fluid dynamics simulations.Thus,one could obtain this type of catalysts from numerous natural diatoms that have inherently intricate morphologies and shapes in micrometer scale.In principle,such catalytic nanocomposites acting as miniaturized industrial catalysts could be employed in microfluidic reactors for process intensification.

Natural high-porous diatomaceous-earth based self-floating aerogel for efficient solar steam power generation

The application of solar steam generation in seawater desalination is an effective way to solve the shortage of fresh water resources.At present,many kinds of photothermal conversion materials have been developed and used as evaporators in seawater desalination.However,some evaporators need additional thermal insulation or water supply devices to achieve efficient photothermal conversion.In addition,their complex,time consuming and no scalable preparation process,high cost of raw materials and poor salt resistance hinder the practical application of these evaporator.Owing to its distinctive nanoporous structure,diatomite as fossilized single-cells algae diatoms is a promising natural silica-based material for seawater desalination.They are taken from sea and that makes true sense to use them in the sea.Herein,we report the first example of synthesis robust three-dimensional(3D)natural-diatomite composite by assembling polyaniline nanoparticles covered diatomite into the polyvinyl alcohol pre-treated melamine foam frameworks and demonstrate its application as new evaporator for seawater desalination.The porous framework does not only improve the sunlight scattering efficiency,but also offer large network of channels for water transportation.The inherent mechanism behind salt desalination process involves the absorption of water molecules on the surface of the internal silica micro-nano pores,and evaporation under the heat induced by the polyaniline absorbed sunlight.Meanwhile,the metal ions are segregated by many available pores and channels to achieve the self-desalting effect.The developed evaporator possesses the superiority of multi-stage pore structure,strong hydrophilicity,low thermal conductivity,excellent light absorption,fast water transportation and salt-resistant crystallization as well as good durability.The evaporation rate without an additional device is found to be 1.689 kg m^(-2)h^(-1)under 1-Sun irradiation,and the energy conversion efficiency is as high as 95%.This work creates a platform and develops the prospect of employing green and sustainable natural-diatomite composite evaporator for practical applications of seawater desalination.

Feasibility of compacted attapulgite/diatomite amended clayey soils as gas barrier materials

Compacted clay liners are extensively used as barriers to control the upward diffusion of vapors of volatile or semi-volatile organic contaminants released from unsaturated contaminated soils at industrycontaminated sites.This study aimed to investigate the gas diffusion barrier performance of compacted clayey soils amended with three agents including attapulgite and diatomite individually,and attapulgite/diatomite mixture.The properties including water retention,volumetric shrinkage,gas diffusion,and unconfined compressive strength were evaluated through a series of laboratory tests of amended compacted clayey soils.The results demonstrate that the decrease in volume proportions of interaggregate pores leads to an increase in unconfined compressive strength(qu).Both hydrophilic groups and microstructures of attapulgite and diatomite result in an increase in water retention percent(Wt)of compacted clayey soil specimens after amendment regardless of the type of agent or initial water content(w0).Furthermore,the ratio of the gas diffusion coefficient(De)to the gas diffusion coefficient in the air(Da)was significantly reduced owing to a decrease in volume proportions of inter-aggregate pores,hydrophilic group,and microstructures of attapulgite and diatomite.Scanning electron microscope analyses revealed that rod-shaped attapulgite filled the inter-aggregate pores formed by clay particles,whereas the disc-shaped diatomite particles,characterized by micropores,failed to obstruct the interaggregate pores due to their larger particle size.Mercury intrusion porosimetry(MIP)analyses showed a reduction in pore volume in the inter-aggregate pores,leading to a reduction in the total pore volume for both the attapulgite and attapulgite/diatomite mixture amended clays,which is in accordance with the scanning electron microscope(SEM)results.The findings are pertinent to the practical application of compacted clay liners as gas barriers against the upward migration of volatile or semi-volatile organic contaminants at contaminated sites.

Diatom and Diatomite: Different Focus on Natural Media to Material Science Path

Bio-silica issued from diatom, a microalgae, is attracted increasing attention in material science thanks to its peculiar nanoarchitecture and related properties with versatile applications. The present work is a deep analysis on morphological and chemical properties of bio-silica issued from fossil origin (diatomaceous earth) and living one (algal paste). An optimization in purification protocol was performed to obtain multiparous bio-silica from its raw media with keeping its original shape entirely. Multiple characterization methods as scanning electronic microscopy (SEM), infrared spectroscopy, x-ray diffraction (DRX), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), nitrogen adsorption and inverse gas chromatography (IGC), were used to check the purification protocol efficiency as well as to gather accurate information on morphology and chemical composition of diatom material obtained in large amount.

Using TiO2-Biocharcoal and TiO2-Diatomite for Photodisinfection in Washing Machine Wastewater

The photodisinfection process using biomolded semiconductor photocatalysts can inactivate bacteria in wastewater washing machine samples. The comparative study evaluated the photocatalyst material titanium dioxide (TiO2) synthesized with diatomite and biocharcoal biotemplate (TiO2-Biocharcoal and TiO2-Diatomite) in photodisinfection processes using domestic washing machine wastewater samples, the results of bacterial inactivation were above 96%. The efficiency of the photodisinfection process was evaluated by counting the number of colonies of the bacteria. Experiments under LED solar lamps presented similar bacterial inactivation, and a correlation with kinetic models. The kinetic study demonstrated a curved regression, indicating a better fit with the Hom model. A tail at the end of the modeling curve indicates the presence of a high concentration of inactive bacteria in the medium, while a shoulder at the beginning of the curve suggests a heterogeneous sample with a high concentration of gram-positive bacteria. The toxicity tests performed with wastewater samples without light exposure indicated low toxicity for both materials. The study presented promising disinfection results for an accessible and efficient photo-sterilization process of water contaminated with bacteria using abundant solar and renewable energy throughout the national territory. .

Hygrothermal Properties of a Composite Based on Clay Soils and Diatomite

The purpose of this paper is to make a contribution to the use of diatomite as a mineral additive in the composition of compressed earth blocks. The aim is to study the influence of diatomite on the hygrothermal behaviour of composites based on clay soils. For this reason, two clay soils with different physicochemical and mineralogical compositions were incorporated with diatomite at percentages ranging from 5% to 50% with a step of 5 to produce compressed earth blocks. After assessing the hydric and thermal characteristics of the composites, it was found that the incorporation of diatomite into the clay matrix favours the absorption of water by capillary action for all the composites. The diatomite-amended blocks subjected to the rain erosion test were less eroded than the unamended blocks. In addition, BYD composites were found to be more resistant than BTD composites, due to the high percentage of clay in T soil. The thermal conductivity of the latter decreases respectively from 0.72 to 0.29 W/m∙K for BTD composites and from 0.52 to 0.21 W/m∙K for BYD composites. This reduction proves the thermal insulating properties of diatomite. Despite the high capillary absorption capacity of these composites, they have good thermal properties, enabling them to be used in the construction of buildings for improved indoor thermal comfort.

Adsorption isotherms for benzene on diatomites from China

In this paper, benzene adsorption isotherm and their hysteresis on two important local diatomites were determined at 25°C, and their silicon hydroxyl group (SiOH) number was determined, their properties were reported, and the relationship between surface structure, surface SiOH number per nm2 and adsorption isotherm with hysteresis was discussed. The specific surface was also calculated from the isotherms, and pore-size distribution was determined.

Flower-, wire-, and sheet-like MnO_2-deposited diatomites:Highly efficient absorbents for the removal of Cr(Ⅵ)

Flower-, wire-, and sheet-like MnO2-deposited diatomites have been prepared using a hydrothermal method with Mn（Ac）2, KMnO4 and/or MnSO4 as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium（VI） were evaluated. It is shown that the IvinO2-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups （especially the wire-like MnO2/diatomite sample）. The wire-like MnO2/diatomite sample showed the best performance in the removal of Cr（VI）, giving the maximum Cr（VI） adsorption capacity of 101 mg/g.

Anti-cracking mechanism of diatomite asphalt and diatomite asphalt mixture at low temperature

A kind of neat asphalt and three kinds of diatomite asphalt are tested using differential scanning calorimetry（DSC）. The anti-cracking mechanism of diatomite asphalt is analyzed by DSC and the thermal stress restrained specimen test（TSRST） of the asphalt mixtures. The results show that the low temperature performance of diatomite asphalt is better than that of neat asphalt. The glass transition temperature can reflect the low temperature performance of the diatomite asphalt better and has a good relationship with breaking temperatures. Besides, the TSRST, the bending test, the compressing test and the contraction coefficient test are used to study the low temperature performance of the diatomite asphalt mixture. The results prove that the low temperature performance of the diatomite asphalt mixture is better than that of the neat asphalt mixture. The critical bending strain energy density and the compressing strain energy density of the diatomite asphalt mixture are greater than those of the neat asphalt mixture. After adding diatomite to the asphalt mixture, the contraction coefficient is reduced. Based on the above results, the anti-cracking mechanism of the diatomite asphalt mixture is analyzed from the angle of contraction performance and breaking energy.

The Role of Diatomite Particles in the Activated Sludge System for Treating Coal Gasification Wastewater

Diatomite is a kind of natural low-cost mineral material. It has a number of unique physical properties and has been widely used as an adsorbent in wastewater treatment. This study was conducted to investigate the aerobic biodegradation of coal gasification wastewater with and without diatomite addition. Experimental results indicated that diatomite added in the activated sludge system could promote the biomass and also enhance the performance of the sludge settling. The average mixed-liquor volatile suspended solids （MLVSS） is increased from 4055 mg.L^-1 to 4518 mg.L^-1 and the average settling volume （SV） are changed only from 45.9% to 47.1%. Diatomite additive could enhance the efficiency of chemical oxygen demand （COD） and total phenols removal from the wastewater. The COD removal increased from 73.3% to near 80% and the total phenols removal increased from 81.4% to 85.8%. The mechanisms of the increase of biomass and pollutants removal may correlates to the improvement of bioavailability and sludge settlement characteristics by diatomite added. Micrograph of the sludge in the diatomite-activated sludge system indicated that the diatomite added could be the carrier of the microbe and also affect the biomass and pollutant removal.

Controlled synthesis of nanosized Si by magnesiothermic reduction from diatomite as anode material for Li-ion batteries

Li-ion batteries(LIBs)have demonstrated great promise in electric vehicles and hybrid electric vehicles.However,commercial graphite materials,the current predominant anodes in LIBs,have a low theoretical capacity of only 372 mAh·g?1,which cannot meet the everincreasing demand of LIBs for high energy density.Nanoscale Si is considered an ideal form of Si for the fabrication of LIB anodes as Si–C composites.Synthesis of nanoscale Si in a facile,cost-effective way,however,still poses a great challenge.In this work,nanoscale Si was prepared by a controlled magnesiothermic reaction using diatomite as the Si source.It was found that the nanoscale Si prepared under optimized conditions(800°C,10 h)can deliver a high initial specific capacity(3053 mAh·g?1 on discharge,2519 mAh·g?1 on charge)with a high first coulombic efficiency(82.5%).When using sand-milled diatomite as a precursor,the obtained nanoscale Si exhibited a well-dispersed morphology and had a higher first coulombic efficiency(85.6%).The Si–C(Si:graphite=1:7 in weight)composite using Si from the sand-milled diatomite demonstrated a high specific capacity(over 700 mAh·g?1 at 100 mA·g?1),good rate capability(587 mAh·g?1 at 500 mA·g?1),and a long cycle life(480 mAh·g?1 after 200 cycles at 500 mA·g?1).This work gives a facile method to synthesize nanoscale Si with both high capacity and high first coulombic efficiency.

Preparation of nano-TiO_2/diatomite-based porous ceramics and their photocatalytic kinetics for formaldehyde degradation

Diatomite-based porous ceramics were adopted as carriers to immobilize nano-TiO2 via a hydrolysis-deposition technique. The thermal degradation of as-prepared composites was investigated using thermogravimetric-differential thermal analysis, and the phase and microstructure were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. The results indicated that the carriers were encapsulated by nano-TiO2 with a thickness of 300-450 nm. The main crystalline phase of TiO2 calcined at 650~C was anatase, and the average grain size was 8.3 nm. The FT-IR absorption bands at 955.38 cm1 suggested that new chemical bonds among Ti, O, and Si had formed in the composites. The photocatalytic （PC） activity of the composites was investigated un- der UV irradiation. Furthermore, the photodegradation kinetics of formaldehyde was investigated using the composites as the cores of an air cleaner. A kinetics study showed that the reaction rate constants of the gas-phase PC reaction of formaldehyde were k = 0.576 mg＇m3·min^-1 and K = 0.048 m3/mg.

Improvement of wood properties by composite of diatomite and “phenol-melamine-formaldehyde” co-condensed resin

We improved the overall performance of fast-growing poplar by utilizing a low-cost, effective and simple method. The fast-growing poplar was modified by a vacuum-pressure impregnation method with three types of modification solutions composed of phe- nol-melamine-formaldehyde （PMF） co-condensed resin, diatomite, and 3-aminopropyl （diethoxy） methylsilane. We measured the weight percent gain （WPG）, bulking, leaching, anti-swelling efficiency （ASE）, wa- ter-repellent effectiveness （WRE）, and oxygen index of the modified specimens. All of the wood physical properties, which are beneficial for human uses, were significantly improved by the treatment. We improved various characteristics of wood and the oxygen index of poplar above 48.6% after the modification using diatomite and PMF co-condensed resin.

Polyhydroxyl-aluminum pillaring improved adsorption capacities of Pb^(2+) and Cd^(2+) onto diatomite

In order to greatly improve adsorption capacity, the diatomite was pillared by polyhydroxyl-aluminum.A series of adsorption tests were conducted to obtain the optimum condition for pillared diatomite synthesis. The scanning electron microscopy （SEM）, Fourier transform infrared spectroscopy （FTIR）, surface area and porosity analyzer and micro-electrophoresis were used to determine pore structure and surface property.The pillared diatomite attaining the optimal adsorption densities （qe） of Pb^2＋ and Cd^2＋ was synthesized with the following conditions： Addition of pillaring solution containing Al3＋-oligomers with a concentration range of 0.1-0.2 mol/L to a suspension containing Na＋-diatomite to obtain the required Al/diatomite ratio of 10 mmol/g; synthesis temperature of 80 ℃ for 120 min; aging at a temperature of 105 ℃ for 16 h. The adsorption capacities of Pb^2＋ and Cd^2＋ on pillared diatomite increase by 23.79% and 27.36% compared with natural diatomite, respectively. The surface property of pillared diatomite is more favorable for ion adsorption than natural diatomite. The result suggests that diatomite can be modified by pillaring with polyhydroxyl-aluminum to improve its adsorption properties greatly.

High adsorption of Cd(Ⅱ)by modification of synthetic zeolites Y,A and mordenite with thiourea

Zeolites Y,A and mordenite(ZY,ZA and ZM)were obtained from diatomite in a template-free system,and the products were modified by thiourea(TU).Characterization studies results indicated that the TU molecules were loaded onto the exterior surfaces of the synthetic zeolites as well as the channels.Elemental analysis and energy-dispersive X-ray spectrometer proved that the TU molecules loaded on to ZA were more than ZY and ZM.Removal of Cd(Ⅱ)was investigated,and itwas found that themodified zeolites have higher removal capacity,modified ZA is especially noticeable.In the adsorption experiments,the effects of various parameters such as sorbent content,contact time,concentration of cadmium solution,pH,selectivity and regeneration were discussed.At the best removal efficiency by modified zeolites,the maximum adsorption capacity is 94.3 mg·g^−1,103.2 mg·g^−1 and 89.7 mg·g^−1 at 25℃,respectively.The sorbents show good efficiency for the removal of Cd(Ⅱ)in the presence of different multivalent cations and have good regeneration effect.For the modified samples,removal experiments take place via ion exchange and complexation processes.

Hydration Characteristics and Humidity Control Performance of Calcium Silicate Board Prepared from Mine Tailing and Diatomite

The feasibility of utilizing molybdenum tailing and diatomite as siliceous materials to prepare calcium silicate board was explored.The influences of molybdenum tailing/diatomite proportion on hydration characteristics,thermal conductivity,water absorption,flexural strength and moisture adsorption-desorption property of calcium silicate board were investigated in detail.The experimental results reveal that molybdenum tailing is environmentally friendly to prepare building materials.The main hydration products in calcium silicate board under autoclaved condition are C-S-H with low crystallinity and tobermorite.Molybdenum tailing is favorable to the formation of tobermorite.The flexural strength and bulk density of the calcium silicate board gradually increase when the content of molybdenum tailing increases.Netlike C-S-H is formed with the increase of diatomite content during autoclaved curing process,resulting in the enhancement of moisture adsorptiondesorption performance and the reduction of thermal conductivity.The optimal content of molybdenum tailing is 20%,furthermore,the flexual strength and thermal conductivity of calcium silicate board at this content meet the Chinese standard JC/T564.1-2008.

Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogenous catalyst

In this study, biodiesel was produced from waste vegetable oil using a heterogeneous base catalyst synthesized by impregnating potassium hydroxide(KOH) onto diatomite. Response surface methodology based on a central composite design was used to optimize four transesterification variables: temperature(30–120 °C), reaction time(2–6 h), methanol to oil mass ratio(10%–50%) and catalyst to oil mass ratio(2.1%–7.9%). A quadratic polynomial equation was obtained to correlate biodiesel yield to the transesterification variables. The diatomite–KOH catalyst was characterized using X-ray diffraction(XRD), Fourier transform infra-red spectroscopy(FTIR) and a scanning electron microscope(SEM) equipped with an energy dispersive X-ray detector(EDS). A maximum biodiesel yield of 90%(by mass) was obtained. The reaction conditions were as follows: methanol to oil mass ratio 30%, catalyst to oil mass ratio 5%, reaction time 4 h, and reaction temperature 75 °C. The XRD, FTIR and SEM(EDS) results confirm that the addition of KOH modifies the structure of diatomite. During impregnation and calcination of the diatomite catalyst the K2 O phase forms in the diatomite structural matrix and the active basicity of this compound facilitates the transesterification process. It is possible to recycle the diatomite–KOH catalyst up to three times. The crucial biodiesel properties from waste vegetable oil are within the American Standard Test Method specifications.

Adsorption of Anionic Dyes onto Chitosan-modified Diatomite

The purpose of this work is to study the possibility of anionic dyes Reactive Red M-8B（RR） and Direct Green B（DG） adsorbed on chitosan-modified diatomite. The characteristics of adsorbent, adsorption isotherms and the influence of adsorption time, temperature and pH were researched in this work. The results show that the mo- dified diatomite had a much better adsorption capability than the natural diatomite. The adsorption capacities of chitosan-modified diatomite for RR and DG were 94.46 and 137.0 mg/g, respectively. Both adsorption time and adsorption temperature provided a positive effect on the dye adsorption. Within the experimental pH range, the adsorbance was enhanced at lower pH but reduced sharply at high pH. On the basis of the experimental results and discussion, electrostatic attraction is considered as the main mechanism of this chemisorption.

Fabrication and Characterization of Diatomite-supported Activated Carbon Functional Ceramic

Using porous diatomite ceramic as carrier and phenolic resin as carbon precursor, the activated carbon functional ceramic with the activated carbon fixed into porous ceramic was prepared by the impregnation load phenolic resin, carbonization and activation isolated air. The influences of impregnation, curing, carbonization, activation etc. on the material property were discussed. The iodine value, SEM, elemental analyzer, BET and spectrum analysis chart were used to characterize the microstructures and performance of material at different conditions. The results showed that the excellent comprehensive property of activated carbon functional ceramic was gained when it adsorbed phenolic resin in 4 h under vacuum condition at curing temperature of 150 ℃ for 0.5 h and carbonization temperature of 600 ℃ for 1.0 h, and then put into 25wt% KOH for 4.0 h at activation temperature of 700 ℃ for 1.5 h. The iodine value is 176.9 mg/g, the specific surface area can reach 86.3 m2/g and the yield of carbonization is 50.48%.

Hydrothermal Solidification of Diatomite and Its Heat Insulating Property

To meet the commercial requirements of inorganic heat insulators,the mixture of diatomite and Ca(OH)2 are evenly dispersed,mold-compacted,and then hydrothermally solidified due to the formation of tobermorite under an autoclaved process.Systematic investigations of the preparation conditions(including mix ratio,autoclaved factors,mold pressure,etc)were carried out to optimize the serving properties of such tobermorite-based products.As a result,a compressive strength of more than 30 MPa was realized for the specimen in high density(about 1.30(g·cm-3)).On the contrary,the specimen in light weight for example 0.63(g·cm-3)typically showed a thermal conductivity of around 0.12(W·m-1·K-1).The present work developed a feasible way to produce and to control the serving properties of diatomite-based heat insulators by a process of hydrothermal solidification,in which the optimized value of Ca/Si ratio was proposed to be 0.6~0.7,while the water content is 25% in weight,and hydrothermal reaction is performed at 180 ℃ for no more than 24 hours.