Hydrothermal hydrogenation/deoxygenation of palmitic acid to alkanes over Ni/activated carbon catalyst

To produce paraffin from hydrogenation/deoxygenation of palmitic acid,model compound of bio-oil obtained by hydrothermal liquefaction(HTL)of microalgae has been an attractive focus in recent years.In order to avoid energy-intensive separation process of water and bio-oil,it is of importance that deoxygenation upgrading of fatty acids under hydrothermal conditions similar to HTL process.Herein,it is the first time to explore the application of activated carbon(AC)-supported non-noble-metal catalysts,such as Ni,Co,and Mo,and so on,in the hydrothermal hydrogenation/deoxygenation of long-chain fatty acids,and the obtained Ni/AC-H(the Ni/AC was further H_(2)pre-reduced)is one of the best catalysts.In addition,it is found that the catalytic activity can be further improved by H_(2)pre-reduction of catalyst.Characterization results that are more low valences of nickel and oxygen vacancy can be obtained after H_(2)pre-reduction,thus significant promoting the deoxygenation especially the decarbonylation pathway of fatty acids.The total alkanes yield can reaches 95.9%at optimal conditions(280℃,360 min).This work confirmed that the low-priced AC-supported non-noble-metal catalysts have great potential compared with the noble-metal catalyst,in hydrothermal upgrading of bio-oil.

Interfacial modification using the cross-linkable tannic acid for highly-efficient perovskite solar cells with excellent stability

Although the performance of perovskite solar cells(PSCs)has been dramatically increased in recent years,stability is still the main obstacle preventing the PSCs from being commercial.PSC device instability can be caused by a variety of reasons,including ions diffusion,surface and grain boundary defects,etc.In this work,the cross-linkable tannic acid(TA)is introduced to modify perovskite film through post-treatment method.The numerous organic functional groups(–OH and C=O)in TA can interact with the uncoordinated Pb^(2+)and I^(-)ions in perovskite,thus passivating defects and inhibiting ions diffusion.In addition,the formed TA network can absorb a small amount of the residual moisture inside the device to protect the perovskite layer.Furthermore,TA modification regulates the energy level of perovskite,and reduces interfacial charge recombination.Ultimately,following TA treatment,the device efficiency is increased significantly from 21.31%to 23.11%,with a decreased hysteresis effect.Notably,the treated device shows excellent air,thermal,and operational stability.In light of this,the readily available,inexpensive TA has the potential to operate as a multipurpose interfacial modifier to increase device efficiency while also enhancing device stability.

Impact of wetting-drying cycles and acidic conditions on the soil aggregate stability of yellow‒brown soil

Soil aggregate is the basic structural unit of soil,which is the foundation for supporting ecosystem functions,while its composition and stability is significantly affected by the external environment.This study was conducted to explore the effect of external environment(wetting-drying cycles and acidic conditions)on the soil aggregate distribution and stability and identify the key soil physicochemical factors that affect the soil aggregate stability.The yellow‒brown soil from the Three Gorges Reservoir area(TGRA)was used,and 8 wetting-drying conditions(0,1,2,3,4,5,10 and 15 cycles)were simulated under 4 acidic conditions(pH=3,4,5 and 7).The particle size distribution and soil aggregate stability were determined by wet sieving method,the contribution of environmental factors(acid condition,wetting-drying cycle and their combined action)to the soil aggregate stability was clarified and the key soil physicochemical factors that affect the soil aggregate stability under wetting-drying cycles and acidic conditions were determined by using the Pearson’s correlation analysis,Partial least squares path modeling(PLS‒PM)and multiple linear regression analysis.The results indicate that wetting-drying cycles and acidic conditions have significant effects on the stability of soil aggregates,the soil aggregate stability gradually decreases with increasing number of wetting-drying cycles and it obviously decreases with the increase of acidity.Moreover,the combination of wetting-drying cycles and acidic conditions aggravate the reduction in the soil aggregate stability.The wetting-drying cycles,acidic conditions and their combined effect imposes significant impact on the soil aggregate stability,and the wetting-drying cycles exert the greatest influence.The soil aggregate stability is significantly correlated with the pH,Ca^(2+),Mg^(2+),maximum disintegration index(MDI)and soil bulk density(SBD).The PLS‒PM and multiple linear regression analysis further reveal that the soil aggregate stability is primarily influenced by SBD,Ca^(2+),and MDI.These results offer a scientific basis for understanding the soil aggregate breakdown mechanism and are helpful for clarifying the coupled effect of wetting-drying cycles and acid rain on terrestrial ecosystems in the TGRA.

Stabilizing perovskite precursors with the reductive natural amino acid for printable mesoscopic perovskite solar cells

Solution processability significantly advances the development of highly-efficient perovskite solar cells.However,the precursor solution tends to undergo irreversible degradation reactions,impairing the device performance and reproducibility.Here,we utilize a reductive natural amino acid,Nacetylcysteine(NALC),to stabilize the precursor solution for printable carbon-based hole-conductorfree mesoscopic perovskite solar cells.We find that I_(2) can be generated in the aged solution containing methylammonium iodide(MI) in an inert atmosphere and speed up the MA-FA^(+)(formamidinium) reaction which produces large-size cations and hinders the formation of perovskite phase.NALC effectively stabilizes the precursor via its sulfhydryl group which reduces I_(2) back to I^(-)and provides H^(+).The NALC-stabilized precursor which is aged for 1440 h leads to devices with a power conversion efficiency equivalent to 98% of that for devices prepared with the fresh precursor.Furthermore,NALC improves the device power conversion efficiency from 16.16% to 18.41% along with enhanced stability under atmospheric conditions by modifying grain boundaries in perovskite films and reducing associated defects.

Construction of core@double-shell structured energetic composites with simultaneously enhanced thermal stability and safety performance

The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues.The coordination complexes which consist of natural polyphenol tannic acid(TA) and Fe~Ⅲ were chosen to construct the inner shell,while the graphene sheets were used to build the outer shell.The resulting CL-20/TA-Fe~Ⅲ/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content,which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell.The phase transition(ε to γ) temperature increased from 173.70 ℃ of pure CL-20 to 191.87℃ of CL-20/TA-Fe~Ⅲ/graphene composites.Meanwhile,the characteristic drop height(H_(50)) dramatically increased from 14.7 cm of pure CL-20 to112.8 cm of CL-20/TA-Fe~Ⅲ/graphene composites,indicating much superior safety performance after the construction of the double-shell structure.In general,this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.

Finite Element Method Simulation of Wellbore Stability under Different Operating and Geomechanical Conditions

The variation of the principal stress of formations with the working and geo-mechanical conditions can trigger wellbore instabilities and adversely affect the well completion.A finite element model,based on the theory of poro-elasticity and the Mohr-Coulomb rock damage criterion,is used here to analyze such a risk.The changes in wellbore stability before and after reservoir acidification are simulated for different pressure differences.The results indicate that the risk of wellbore instability grows with an increase in the production-pressure difference regardless of whether acidification is completed or not;the same is true for the instability area.After acidizing,the changes in the main geomechanical parameters(i.e.,elastic modulus,Poisson’s ratio,and rock strength)cause the maximum wellbore instability coefficient to increase.

Comparative Effect of Adding Synthetic Citric Acid to Natural Lemon Juice (Citrus aurantiifolia) on the Stability of Hibiscus Drinks Stored at 4°C and 37°C

The general objective of the work is to compare the effect of the addition of synthetic citric acid compared to the addition of natural fruit juice of Citrus aurantiifolia on the conservation of drink based on red chalice H. sabdariffa. The tests were carried out over a period of 5 weeks at 4°C and 37°C with seven batches of beverage samples prepared at the rate of a calyx/water ratio of 1/40 (kg·kg-1) and added respectively citric acid at 1, 2 and 4 g·L-1 and lemon juice at 10, 20 and 40 mL·L-1. The characterization of the different batches of beverages was carried out from day one. A follow-up of the residual anthocyanin content and the intensity of the red coloring were carried out over five weeks. The anthocyanin concentration was determined by the pH-differential method. The red color degradation index is determined based on the CIELAB color system (L*, a*, b* and L*). R and Minitab 18 software was used for data processing. The results of the monitoring of the parameters showed that the concentration of 1 g AC L-1 retains 2.7 mg more of the anthocyanins than adding 10 mL JC L-1 and longer maintains red color when stored at 4°C and 37°C/5 weeks. The 2 g AC L-1 and 4 g AC L-1 ratios have the same effects as the addition of 20 and 40 mL of lemon juice, all accelerating the degradation of anthocyanins and the red color. After 5 weeks of storage at 37°C, the effect of the temperature combined with the increase in the acidity of the samples (2 to 4 g AC L-1 and 20 to 40 ml JC L-1), have accelerated the total disappearance of the red color on all samples.

Removal of arsenic from acid wastewater via sulfide precipitation and its hydrothermal mineralization stabilization

To achieve a safe treatment of arsenic-containing acid wastewater,a new process was proposed,including arsenic removal via sulfide precipitation and hydrothermal mineralization stabilization.Under optimal conditions of sulfide precipitation,99.65%of arsenic from wastewater was precipitated in the form of amorphous As2S3.The As leaching concentration of amorphous As2S3 in TCLP(toxicity characteristic leaching procedure)test was up to 212.97 mg/L,therefore,hydrothermal mineralization was adopted to improve the stability of amorphous As2S3.The results showed that the As leaching concentration of mineralized As2S3 was only 4.82 mg/L.Furthermore,the amorphous As2S3 could be transformed into crystallized As2S3(orpiment)in the presence of mineralizer Na2SO4.Simultaneously,the As leaching concentration of crystallized As2S3 was further reduced to 3.86 mg/L.Hydrothermal mineralization was an effective method for the stabilization of As2S3.Therefore,this process has a greater application in the treatment of arsenic-containing wastewater.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Binuclear Copper(Ⅱ) Complex with 3-(Pyridin-2-yl)-1,2,4-triazole

One novel binuclear copper（Ⅱ） complex [Cu 2 （Hpt） 2 （CO 3） 2 （H 2 O） 2 ]·H 2 O with copper carbonate and 3-（pyridin-2-yl）-1,2,4-triazole （Hpt） was hydrothermally synthesized and characterized by IR and X-ray diffraction analysis.The complex crystallizes in triclinic,space group P2 1 /n with a=0.6862（1）,b=0.7805（1）,c=1.1983（2） nm,α=72.03（2）,β=107.72（3）,γ=75.28（2）o,V=0.5884 nm 3,D c=2.105 g/cm 3,Z=1,F（000）=357,GOOF=1.041,the final R=0.01859 and wR=0.04348.The whole molecule is composed of two cooper ions,two Hpt molecules,two carbonate and three water molecules,forming a binuclear structure.The crystal structure shows that the cooper ion is coordinated with three nitrogen atoms from two Hpt molecules,two oxygen atoms from one carbonic acid and one water molecule,forming a distorted square pyramidal geometry.The TG analysis result shows that the title complex is stable under 131.0 ℃.

Study on Hydrothermal Stability and Catalytic Activity of Al-SBA-15 Mesoporous Materials Prepared by Impregnation Method

The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.

Enhancing hydrothermal stability of nano-sized HZSM-5 zeolite by phosphorus modification for olefin catalytic cracking of full-range FCC gasoline

In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.

A reconstruction strategy for the synthesis of Cu-SAPO-34 with excellent NH-SCR catalytic performance and hydrothermal stability

A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region,high solid yield,and tunable Si and Cu contents.Cu-rich SAPO-34 was prepared from a Cu-amine complex,which acted as a precursor and Cu source for the reconstruction synthesis.The role of the Cu-amine complex as a template was restricted,which allowed easier control over the Cu and Si contents than in the previously reported"one-pot"synthesis method.Characterization of the material revealed that the Si(4Al)coordination environment dominates the synthesized Cu-SAPO-34 catalysts.High-temperature hydrothermal treatment increased the isolated Cu2+content slightly,and the acid sites in the low-silica catalyst are more resistant to hydrothermal treatment than those of the existing catalysts.The obtained materials,especially the low-silica Cu-SAPO-34 sample,exhibit excellent catalytic activity and hydrothermal stability for the selective catalytic reduction of NOx by NH3(NH3-SCR).In addition,the influence of the catalyst acidity on the NH3-SCR reaction was also investigated and is discussed.The high synthetic efficiency and outstanding catalytic performance make Cu-SAPO-34 synthesized by the reconstruction method a promising catalyst for the NH3-SCR process.

Hydrothermal Synthesis, Crystal Structure,Thermal Stability and Photophysical Property of a Novel Zinc Complex with Mixed Ligands

A novel metal-organic coordination complex [Zn（CHIP）（AIC）]n （1, CHIP = 2-（4- chlorophenyl）-lH-imidazo[4,5-f][1,10]phenanthroline, A1C = 5-amino-isophthalic acid） has been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric （TG） analysis, infrared spectrum （IR） and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 18.259（5）, b = 17.191（4）, c = 16.371（4） A, V= 4717（2） A3, C27H16C1NsOnZn, Mr= 575.29, Dc = 1.620 g/cm3, p（MoKa） = 1.202 mm-1, F（000） = 2335, Z = 8, the final R = 0.032 and wR = 0.074 for 4723 observed reflections （I 〉 2σ（I））. Single-crystal X-ray diffraction reveals that 1 exhibits one-dimensional （1D） double chains, which are linked by H-bond intersections into a 2D structure. TG analysis shows clear weight loss due to the decomposition of different ligands. The luminescent properties for the ligand and complex 1 were also studied.

Investigation of low-temperature hydrothermal stability of Cu-SAPO-34 for selective catalytic reduction of NO_x with NH_3

The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.

Hydrothermal Synthesis and Thermal Stability of Natural Mineral Lindgrenite

A natural mineral, lindgrenite Cu3 （ MoO4 ）2 （ OH）2, was synthesized from a mixture of sodium molybdate, copper sulfate, and morpholine in water under autogenous pressure at 170 ℃. The crystal structure of the mineral was determined and the final refinement for 791 observed reflections with Ⅰ 〉 2σ（Ⅰ） gave R1 = 0. 0205 and wR2 = 0. 0496. The thermal stability of the mineral was investigated by using TG-DTA and variable-temperature in situ X-ray diffraction（XRD） techniques. The crystalline Cu3Mo2O9 was obtained when the mineral underwent thermal dehydration at a temperature ranging from 300 to 400 ℃, and the mixture of MoO3 and CuO was formed through decomposition of Cu3Mo2O9 at a temperature ranging from 650 to 700 ℃. Therefore, the structure of the mineral was thermally unstable at above 300 ℃, suggesting that Lindgrenite was likely formed via the hydrothermal route occurring in the nature.

Gas separation using sol–gel derived microporous zirconia membranes with high hydrothermal stability

A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.

Synthesis of Ordered Cubic Periodic Mesoporous Silica with High Hydrothermal Stability

1 Introduction Since its first discovery in 1992, ordered mesoporous silica material with large pore size, high surface area, and high pore volume has attracted great attention for the potentially wide application in catalysis, adsorption, separation, and ion exchange, etc. However, the poor hydrothermal stability of mesoporous silica has limited its wide application in industry. Therefore, in the last 10 years, many studies have been dedicated to improving the hydrothermal stability of mesoporous silica. Xiao et al.

Onset and Stability of Thermally-Driven Fluid Convection in a Vertical Rock Crack and Their Implication for Hydrothermal Ore-Forming Processes

Dynamic equations controlling the thermally-driven fluid convection in a single rock crack are established in the paper . The critical criteria for the onset of convection in such a configuration are found by linear dynamic analysis of the equations and the stability of the convection discussed by nonlinear analysis method . The research demonstrates that the critical Rayleigh number has a magnitude 103. While the Rayleigh number R of real ore-forming fluids exceeds this value , the convection happens , and as R becomes larger , the fluid convection pattern develops from nonequilibrium steady states to double-periodically produced limit cycles and eventually to chaos (turbulences ).The implication of these dynamic analyses for the ore-forming processes of late-magma tic hydrothermal deposits is also discussed in the paper .

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of [Ni(phen)_3]·(C_8H_(12)O_4)·(H_2O)_(14)

One novel complex [Ni（phen）3],（C8H12O4）·（H2O）14 with hexane dicarboxylic acid and 1,10-phenanthroline has been hydrothermally synthesized and characterized. Crystal data： monoclinic, space group C2/c, a = 2.3475（5）, b = 1.2208（2）, c = 1.9499（4） nm, β= 114.682（3）°, V = 5.0778（16） nm^3, Dc = 1.339 g/cm^3, Z = 4,μ（MoKa） = 0.458 mm^-1, F（000） = 2168, GOOF = 1.014, R = 0.0401 and wR = 0.0961. The nickel（H） center in the title complex is coordinated with six nitrogen atoms of three 1,10-phenanthroline molecules, giving a distorted octahedral coordination geometry. However, the nickel（Ⅱ） ion does not coordinate to the hexane dicarboxylic acid. The complex molecules form a 3D structure through hydrogen bonds. TG analysis shows that the title complex is stable below 240.0 ℃.

A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater

Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing free radicals, the stability of catalysts is often insufficient, which has become a bottleneck in the application of CWAO. In this paper, a copper-based catalyst with excellent hydrothermal stability was designed and prepared. TiO_(2) with excellent stability was used as the carrier to ensure the longterm anchoring of copper and reduce the leaching of the catalyst. The one pot sol–gel method was used to ensure the super dispersion and uniform distribution of copper nanoparticles on the carrier, so as to ensure that more active centers could be retained in a longer period. Experiments show that the catalyst prepared by this method has good stability and catalytic activity, and the catalytic effect is not significantly reduced after 10 cycles of use. The oxidation degradation experiment of m-cresol with the strongest biological toxicity and the most difficult to degrade in coal chemical wastewater was carried out with this catalyst. The results showed that under the conditions of 140℃, 2 MPa and 2 h, m-cresol with a concentration of up to 1000 mg·L^(-1) could be completely degraded, and the COD removal rate could reach 79.15%. The biological toxicity of wastewater was significantly reduced. The development of the catalyst system has greatly improved the feasibility of CWAO in the treatment of refractory wastewater such as coal chemical wastewater.