Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

Research progress on catalysts for organic sulfur hydrolysis: Review of activity and stability

The removal of organic sulfur through catalytic hydrolysis is a significant area of research in the field of desulfurization.This review provides an overview of recent advancements in catalytic hydrolysis technology of organic sulfur,including the activity,stability,and atmosphere effects of hydrolysis catalysts.The emphasis is on strategies for enhancing hydrolysis activity and anti-oxygen poisoning property of catalysts.Surface modification,metal doping and nitrogen doping have been found to improve the activity of catalysts.Alkaline components modification is the most commonly used method,the formation of oxygen vacancies through metal doping and creation of nitrogen basic sites through nitrogen doping also contribute to the hydrolysis of organic sulfur.The strategies for anti-oxygen poisoning are discussed in a systematic manner.The structural regulation of catalysts is beneficial for the desorption and diffusion of hydrogen sulfide(H_(2)S),thereby effectively inhibiting its oxidation.Nitrogen doping and the addition of electronic promoters such as transition metals can protect active sites and decrease the number of active oxygen species.These methods have been proven to enhance the anti-poisoning performance of catalysts.Additionally,this article summarizes how different atmospheres affect the activity of hydrolysis catalysts.The objective of this review is to pave the way for the development of efficient,stable and widely used catalysts for organic sulfur hydrolysis.

CAOSA-extracted lignin improves enzymatic hydrolysis of cellulose

The conversion of biomass into sugar platform compounds is very important for the biorefinery industry.Pretreatment is essential to the biomass of the sugar platform,however,the lignin obtained by pretreatment,as a key part of lignocellulose,generally has a passive effect on the enzymatic hydrolysis of cellulose into sugars.In this study,p-TsOH(p-toluenesulfonic acid),DES(Deep eutectic solvent)and CAOSA(cooking with active oxygen and solid alkali)pretreatment ways were used to fraction lignin from bamboo biomass.After CAOSA treatment,the hydrolysis efficiency of the pulp was 95.57%.Moreover,the effect of different treatment methods on lignin properties was studied and the promotion effect of lignin was investigated by adding it to the cellulose enzymatic hydrolysis system.In this work,the results showed that CAOSA-extracted lignin with lower D(1.31-1.25)had a better adsorption effect on the enzyme protein.p-TsOH-extracted lignin with a larger S/G ratio enhanced the inhibition of enzymatic hydrolysis.In addition,the presence of-COOHs in lignin could reduce its inhibitory effect on cellulose saccharification.

An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis

Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.

In situ formed Mg(BH_(4))_(2) for improving hydrolysis properties of MgH_(2)

The hydrolysis of MgH_(2) delivers high hydrogen capacity(15.2 wt%),which is very attractive for real-time hydrogen supply.However,the formation of a surface passivation Mg(OH)_(2) layer and the large excess of H_(2)O required to ensure complete hydrolysis are two key challenges for the MgH_(2) hydrolysis systems.Now,a low-cost method is reported to synthesize MgH_(2)@Mg(BH_(4))_(2) composite via ball-milling MgH_(2) with cheap and widely available B_(2)O_(3)(or B(OH)_(3)).By adding small amounts of B_(2)O_(3),the in-situ formed Mg(BH_(4))_(2) could significantly promote the hydrolysis of MgH_(2).In particular,the MgH_(2)–10 wt%B_(2)O_(3) composite releases 1330.7 mL·g^(−1) H_(2)(close to 80%theoretical hydrogen generation H_(2))in H_(2)O and 1520.4 mL·g^(−1) H_(2)(about 95%)in 0.5 M MgCl_(2) in 60 min at 26℃ with hydrolysis rate of 736.9 mL·g^(−1)·min^(−1) and 960.9 mL·g^(−1)·min^(−1) H_(2) during the first minute of the hydrolysis,respectively.In addition,the MgCl_(2) solution allows repeated use by filtering and exhibits high cycle stability(20 cycles),therefore leading to much reduced capacity loss caused by the excess H_(2)O.We show that by introducing B_(2)O_(3) and recycling the 0.5 M MgCl_(2) solution,the system hydrogen capacity can approach 5.9 wt%,providing a promising hydrogen generation scheme to supply hydrogen to the fuel cells.

Preliminary Study on the Treatment Efficiency of Pasteurized Lime Thermal Alkaline Hydrolysis for Excess Activated Sludge and Reduction of Tetracycline Resistance Genes

Thermal alkaline hydrolysis is a common pretreatment method for the utilization of excess activated sludge(EAS).Owing to strict environment laws and need for better energy utilization,new methods were developed in this study to improve the efficiency of pretreatment method.Direct thermal hydrolysis(TH),pasteurized thermal hydrolysis(PTH),and alkaline pasteurized thermal hydrolysis(PTH+CaO and PTH+NaOH)methods were used to treat EAS.Each method was compared and analyzed in terms of dissolution in ammonium nitrogen(NH_(4)^(+)-N)and soluble COD(SCOD)in EAS.Furthermore,the removal of tetracycline resistance genes(TRGs)and class 1 transposon gene intI1 from EAS was investigated.The NH_(4)^(+)-N and SCOD concentrations in EAS treated by PTH were 1.24 and 2.58 times higher than those of TH.However,the removal efficiency of total TRGs and intI1 between the groups was comparable.The SCOD concentration of the PTH+NaOH group was 4.37 times higher than that of the PTH group,and the removal efficiency of total TRGs was increased by 9.52%compared with that by PTH.The NH_(4)^(+)-N and SCOD concentrations of the PTH+CaO group could reach 85.04%and 92.14%of the PTH+NaOH group,but the removal efficiency of total TRGs by PTH+CaO was 19.78%lower than that by PTH+NaOH.Thus,to reduce the financial cost in actual operation,lime(CaO)can be used instead of a strong alkali(NaOH),and pasteurized steam at 70℃ instead of conventional high-temperature heating to treat EAS.This study provides a reference for the development of alkaline hydrolysis under moderate temperatures along with the removal of TRGs in EAS.

Enzymatic hydrolysis of silkworm pupa and its allergenicity evaluation by animal model with different immunization routes

Silkworm pupa is a nourishing food with high nutritional value,but its consumption has been greatly limited given its allergenicity.Enzyme hydrolytic technique is recognized as an effective method to reduce the allergenicity of protein.In this study,we aimed to investigate the effect of enzymolysis on the allergenicity of silkworm pupa.Crude silkworm pupa protein was extracted through alkali extraction and acid precipitation,which included 5 proteins with the molecular weights ranging from 34 kDa to 76 kDa,and silkworm pupa were then hydrolyzed by alkaline protease.The allergenicity of silkworm pupa protein and its enzymatic hydrolysates was evaluated by establishing BALB/c mice model,and the mice were immunized via intragastric gavage and intraperitoneal injection,respectively.The results indicated that the intraperitoneal inj ection immunization route induced more by detecting with antibodies,histamine and Th2-related cytokines.Moreover,mice treated with silkworm pupa protein peptide displayed no obvious allergic symptoms,indicating that enzyme hydrolytic technique could significantly reduce the allergenicity of silkworm pupa.

Oxygen vacancy defects engineering on Cu-doped Co_(3)O_(4) for promoting effective COS hydrolysis

The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.

Structural and antioxidative properties of royal jelly protein by partial enzymatic hydrolysis

The objective of this study was to investigate the structural and antioxidative properties of royal jelly protein(RJP)at different degrees of hydrolysis(DH)by partial enzymatic hydrolysis. RJP was hydrolyzed by alcalase for 0 min, 15 min, 1 h, 5 h and 8 h to obtain hydrolysates at DH of 5.34%, 11.65%, 15.19%, 21.38% and 23.91%, respectively. With the increased DH, the RJP hydrolysates showed elevated antioxidative activities. The molecular weight of RJP hydrolysates was significantly decreased but their primary backbone kept unchanged. Analysis of circular dichroism spectra revealed that the enzymolysis reduced the content of α-helix but increased the contents of β-sheet, β-turn and random coil. Meanwhile, the surface hydrophobicity and fluorescence intensity of RJP hydrolysates were decreased and a red shift occurred. As the enzymolysis continued, the surface morphology of RJP was gradually changed from a sheet-like structure into microparticles. Changes in antioxidative activities and structures generally followed a DH-dependent manner, however these changes became insignificant for samples at DH beyond 20%. Taking into consideration of both effectiveness and productivity, the optimum enzymatic duration was determined at 5 h.

Hydrogel-based catalysts for hydrogen generation by the hydrolysis of B–H compounds under external physical fields

Hydrogen is a popular clean high-energy-density fuel.However,its utilization is limited by the challenges toward low-cost hydrogen production and safe hydrogen storage.Fortunately,these issues can be addressed using promising hydrogen storage materials such as B–H compounds.Hydrogen stored in B–H compounds can be released by hydrolysis at room temperature,which requires catalysts to increase the rate of the reaction.Recently,several effective approaches have been developed for hydrogen generation by catalyzing the hydrolysis of B–H compounds.This review summarizes the existing research on the use of nanoparticles loaded on hydrogels as catalysts for the hydrolysis of B–H compounds.First,the factors affecting the hydrolysis rate,such as temperature,p H,reactant concentration,and type of nano particles,were investigated.Further,the preparation methods(in situ reduction,one-pot method,template adsorption,etc.)for the hydrogel catalysts and the types of loaded catalysts were determined.Additionally,the hydrogel catalysts that can respond to magnetic fields,ultrasound fields,optical fields,and other physical fields are introduced.Finally,the issues and future developments of hydrogel-based catalysts are discussed.This review can inspire deeper investigations and provide guidance for the study of hydrogel catalysts in the field of hydrogen production via hydrolysis.

Effect of acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust in subcritical water

The effects of sulfuric acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust were investigated in this study.Sulfuric acid could act as an acidic catalyst to depolymerize holocellulose through cleavage of the glycosidic bonds,the dissociation energies of which were supplied by the impact of a ball on pine sawdust,during milling.The destruction of glycosidic and hydrogen bonds in pine sawdust resulted in a decrease of crystallinity and an increase of water solubility.The sulfuric acid could promote the hydrolysis of holocellulose and its hydrolysis products.It also destroyed the chemical linkages between holocellulose and lignin during ball milling.The cleavage of chemical linkages with holocellulose made lignin more difficult to hydrolyze in subcritical water,and higher activation energy was needed to hydrolyze pretreated pine sawdust at higher reaction temperatures.It also led to the formation of glucose char and aromatic-linked polymer char from the hydrolysis products of holocellulose.

Effects of Potassium Ferrate and Low-Temperature Thermal Hydrolysis Co-Pretreatment on the Hydrolysis and Anaerobic Digestion Process of Waste Activated Sludge

This study evaluated the effect of potassium ferrate(PF)and low-temperature thermal hydrolysis co-pretreatment on the promotion of sludge hydrolysis process and the impact on acid production in the subsequent anaerobic digestion process.The analytical investigations showed that co-pretreatment significantly facilitated the hydrolysis process of the sludge and contributed to the accumulation of short-chain fatty acids(SCFAs).The pretreatment conditions under the optimal leaching of organic matter from sludge were hydrothermal temperature of 75℃,hydrothermal treatment time of 12 h,and PF dosage of 0.25 g g^(−1)TSS(total suspended solids),according to the results of orthogonal experiments.By pretreatment under proper conditions,the removal rate of soluble chemical oxygen demand(SCOD)achieved 71.8%at the end of fermentation and the removal rate of total phosphorus(TP)was 69.1%.The maximum yield of SCFAs was 750.3 mg L^(−1),7.45 times greater than that of the blank group.Based on the analysis of the anaerobic digestion mechanism,it was indicated that the co-pretreatment could destroy the floc structure on the sludge surface and improve organic matter dissolving,resulting in more soluble organic substances for the acidification process.Furthermore,microbial community research revealed that the main cause of enhanced SCFAs generation was an increase in acidogenic bacteria and a reduction of methanogenic bacteria.

Catalytic Hydrolysis of CFC-12 over MoO_(3)/ZrO_(2)-TiO_(2)

Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst in polycrystalline state could be clearly observed by transmission electron microscopy(TEM).Mesopores were detected by N2 adsorption-desorption isotherms which further confirmed the MoO_(3)/ZrO_(2)-TiO_(2)structural characteristics of catalyst.The results of NH_(3)-TPD showed that the calcination temperatures had a great influence on the acidity of the catalyst,and the weak acidic site had a strong catalytic activity for the catalytic hydrolysis of CFC-12.Moreover,ZrO_(2)-TiO_(2)was highly dispersed in the MoO_(3)framework,suggested by powder X-ray diffraction(XRD)and N_(2)adsorption-desorption results.The effects of the catalyst calcination temperatures on the conversion rate of CFC-12 were studied.The effects of catalytic hydrolysis temperatures and water vapor concentration on the catalytic hydrolysis rate of CFC-12 were also studied.The solid acid MoO_(3)/ZrO_(2)-TiO_(2)was calcined at 500℃for 3 h at a catalytic hydrolysis temperature of 400℃and water vapor concentration of 83.18%,and catalytic hydrolysis rate of CFC-12 reached 98.65%.The hydrolysis rate of CFC-12 remained above 65.34%after 30 hours continuous reaction.

Glucosinolates and Their Hydrolysis Products in Arabidopsis thaliana Influence Performance and Feeding Choice of Pieris rapae and Spodoptera exigua

Glucosinolates and their hydrolysis products, found in plants of the order Brassicales, are well-known for their defensive properties against insect herbivores. Arabidopsis thaliana (Col-0) genetic lines with mutations that modify the type of glucosinolates (i.e. myb28myb29 and cyp79B2cyp79B3 are deficient in the production of aliphatic and indolyl glucosinolates, respectively) make it possible to test for the specific effects of these secondary chemicals on insect herbivores. The Pad3 mutant (deficient in camalexin), which has a role in resistance to pathogens, was also tested. Likewise, the effects of different glucosinolate hydrolysis products can be evaluated using genetically modified (GM) lines of the wild type Col-0 ecotype, which naturally produces isothiocyanates. These GM lines include the nitrile-producing 35S: ESP and the double knockout tgg1tgg2, which virtually lacks hydrolysis products. In both no-choice and choice experiments, the crucifer specialist Pieris rapae was virtually unaffected by differences in the type of glucosinolates or hydrolysis products. In contrast, the generalist insect Spodoptera exigua had statistically significant increases in pupae/adult weight and faster developmental times when reared on mutants deficient in the production of aliphatic and indolyl glucosinolates and their hydrolysis products. There were no differences in the performance of either insect species when reared on wild type Col-0 or Pad3. Results from feeding choice trials showed that Pieris rapae had no statistically significant preference for any of the genetic lines. In contrast, Spodoptera exigua had a significant feeding preference for the double mutant tgg1tgg2. This study provides evidence that variation in the type of glucosinolates and their hydrolysis products can influence insect performance and feeding choices, and that responses are species-specific.

Effects of Dilute Acid-intensified Hydrolysis on Fermentative Biohydrogen Production Capacity of Maize Stalk

[Objective] This study was to explore the effects of dilute acid hydrolysis on fermentative biohydrogen production capacity of maize stalk. [Method] Using maize stalks subjected to mechanical disintegration,steam explosion and dilute acid hydrolysis as experimental materials,we measured and analyzed the effects of different treatments and particle size of maize stalk were analyzed. [Result] The optimal fermentative biohydrogen production was found under following parameters：pretreatment of 0.8% dilute H2SO4 following steam explosion,particle size of maize stalk of 0.425-0.850 mm,liquid-solid ratio [0.8% H2SO4 （M）：stalk （W）] of 10：1. [Conclusion] Post steam explosion,dilute 0.8% dilute H2SO4 intensified hydrolysis on maize stalk could produce fermentative biohydrogen production capacity.

Preparation and Characterization of Nanometer TiO_2 by Hydrolysis Precipitation Method

Nanometer TiO 2 powders were obtained from TiOSO 4 and studied by XRD, TEM and BET. The result indicated that pH and heat treatment temperature have great effects on their grain size and crystal phase structure. Annealed at 500 ℃, nanometer TiO 2 with a specific surface area of 101.39 m 2 ·g -1 and a grain size about 10 nm were obtained(pH=5); and with a specific surface area of 95.48 m 2 ·g -1 and a grain size about 30 nm were obtained(pH=10). The research indicated that crystal phase transformation of rutile at 750 ℃made great promotion in grain size growth.

Influence of K + on the Coupling Between ATP Hydrolysis and Proton Transport by the Plasma Membrane H +_ATPase from Soybean Hypocotyls

The plasma membrane vesicles were purified from soybean (Glycine max L.) hypocotyls by two_phase partitioning methods. The stimulatory effects of K + on the coupling between ATP hydrolysis and proton transport by the plasma membrane H +_ATPase were studied. The results showed that the proton transport activity was increased by 850% in the presence of 100 mmol/L KCl, while ATP hydrolytic activity was only increased by 28.2%. Kinetic studies showed that K m of ATP hydrolysis decreased from 1.14 to 0.7 mmol/L, while V max of ATP hydrolysis increased from 285.7 to 344.8 nmol Pi·mg -1 protein·min -1 in the presence of KCl. Experiments showed that the optimum pH was 6.5 and 6.0 in the presence and absence of KCl, respectively. Further studies revealed that K + could promote the inhibitory effects of hydroxylamines and vanadates on the ATP hydrolytic activity. The above results suggested that K + could regulate the coupling between ATP hydrolysis and proton transport of the plasma membrane H +_ATPase through modulating the structure and function of the kinase and phosphatase domains of the plasma membrane H +_ATPase.

Hydrolysis Mechanism of the NAMI-A-type Antitumor Complex （HL）[trans-RuCl4L（dmso-S）] （L=1-methyl-l,2,4-triazole）

The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.

Theoretical Studies on Mechanism and Rate Constant of Gas Phase Hydrolysis of Glyoxal Catalyzed by Sulfuric Acid

The gas phase hydration of glyoxal （HCOCHO） in the presence of sulfuric acid （H2SO4） were studied by the high-level quantum chemical calculations with M06-2X and CCSD（T） theoretical methods and the conventional transition state theory （CTST）. The mechanism and rate constant of the five different reaction paths are consid- ered corresponding to HCOCHO＋H2O, HCOCHO＋H2O… H2O, HCOCHO… H2O＋H2O, HCOCHO＋H2O… H2SO4 and HCOCHO… H2O＋H2SOa. Results show that H2SO4 has a strong catalytic ability, which can significantly reduce the energy barrier for the hydration reaction of glyoxal. The energy barrier of hydrolysis of glyoxal in gas phase is lowered to 7.08 kcal/mol from 37.15 kcal/mol relative to pre-reactive complexes at the CCSD（T）/6- 311＋＋G（3df, 3pd）//M06-2X/6-311＋＋G（3df, 3pd） level of theory. The rate constant of the H2SO4 catalyzed hydrolysis of glyoxal is 1.34×10-11 cm3/（molecule.s）, about 1013 higher than that involving catalysis by an equal number of water molecules, and is greater than the reaction rate of glyoxal reaction with OH radicals of 1.10×10-11 cm3/（molecule·s） at the room temperature, indicating that the gas phase hydrolysis of glyoxal of H2SO4 catalyst is feasible and could compete with the reaction glyoxal＋OH under certain atmospheric condi- tions. This study may provide useful information on understanding the mechanistic features of inorganic acid-catalyzed hydration of glyoxal for the formation of oligomer.

STUDY ON HYDROLYSIS RESISTANT POLYCARBONATE POLYURETHANE EPOXY RESIN BLENDS

This paper studies the structure and properties of the polycarbonate polyurethane epoxy resin (PCPU EP) blends being resistant to hydrolysis.The samples were analyzed by an infrared spectrometer,a differential scanning calorimeter,a scanning electron microscope and a dynamic viscoelastometer.The results show that PCPU EP blends have excellent resistance to hydrolysis and mechanical properties at the ratio of PCPU to EP equal to 10/100 (wt/wt).