Inhibiting effect of[HOEmim][BF_4]and[Amim]Cl ionic liquids on the cross-linking reaction of bituminous coal

In order to reduce the hazard of coal spontaneous combustion,the cross-linking reaction between O-containing functional groups of coal should be inhibited.So the inhibitory effect of an ionic liquid(IL) on the cross-linking reaction was studied.The O-containing functional groups change the weight loss and H_2O,CO_2,CO yields of bituminous coal before and after[H0Emim][BF_4]and[Amim]Cl pre-treatment and were detected by Fourier Transform Infrared spectroscopy(FT1R) and Thermo Gravimetric(TC) analysis.The results show that | AmimjCI has a weaker ability to inhibit the cross-linking reaction of bituminous coal compared to[HOEmim][BF_4].Besides,based on Quantum Chemistry calculation,it was found that the different inhibiting effects of |H0Emim][BF_4]and[Amim]Cl are greatly related to their anions and the H linked with C2 atom on the imidazole ring.The H-donor ability of coal will be enhanced by[HOEmim][BF_4]leading to a weaker cross-linking reaction of coal.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

THE STUDY OF THE REACTION OF THE QUASI-AROMATIC COMPLEX [Ni(PnAO)-6H]^(?)WITH FORMALDEHYDE: KINETICS AND MECHANISM

The kinetics of the reaction of [Ni(PnAO)—6H]° with formaldehyde was studied in H_2O—CH_3OH solution under neutral condition and a complicated mechanism with three steps including competitive, consecutive and reverse reactions was proposed.

AB INITIO STUDIES ON THE REACTION MECHANISH OF CYCLOADDITION OF KETENE AND FORMALDEHYDE

The cycloaddition reaction of ketene and formaldehyde,lesding to 2- oxetanone,has been studied theoretically by means of RHF/3-21G.This reaction is believed to be nonsynchronous but concerted,taking place through a twisted four membered ring transition state.Two types of frontier orbital interactions are involved in this reaction.The activation barrier is calculated to be 123.1KJ/mol (MP2/3-21G result).

Formaldehyde decomposition of air purification functional interior wall paint

A novel nano-TiO2-xNx composite was used as photocatalyst and added to the interior wall paint. The average diameter of nano-TiO2-xNx was about 20 nm. The majority crystal component of the sample was anatase and its optical absorption edge was shifted from 387 nm to 520 nm significantly. Nano-composite paint containing different dosage of nano- TiO2-xNx was investigated to study the properties of formaldehyde decomposition in the air. Testing results show that the formaldehyde decomposition ratio of that nano-paint can almost reach above 80%, especially for that of the paint containing 3% （w/w） nano-TiO2-xNx which exceeded 90%. The primary investigation on the reaction kinetics of photocatalytic formaldehyde decomposition indicated that the experiment data well fit the model of first-order reaction kinetics.

Addition Mechanisms of Phenol toward Formaldehyde under Acidic Condition: a Theoretical Investigation

The reaction mechanisms of phenol with formaldehyde in the first and second addition at the ortho- and para-position in acid solution were theoretically investigated at the PW91/DNP level with solvent effects included. The reaction of phenol with protonated methanediol firstly forms an adduct intermediate, via a SN2 mechanism with a water molecule as the leaving group. From the adduct intermediate, there are two reaction channels involving a proton transfer to form the addition products. One is that a proton directly transfers via a four-membered ring transition state with a notable energy barrier （Four-member mechanism）. Another mechanism involving a water molecule as catalyst to mediate the proton transfer （WCP mechanism）, is a barrierless process, indicating that the formation of the adduct intermediate, the first reaction step, is rate-limiting. The reaction products are free hydroxymethyl phenols and/or hydroxybenzy carbocation （HOC6H4CH2＋） which plays an important role in the following formation of methylene and methylene ether linkages. The second addition reactions between formaldehyde and hydroxymethyl phenol at all possible reaction sites of the phenol ring in acid solution were also investigated and discussed.

Light-Induced Dynamic Stability of Oxygen Vacancies in BiSbO_(4) for Efficient Photocatalytic Formaldehyde Degradation

Defect engineering has been regarded as a versatile strategy to maneuver the photocatalytic activity.However,there are a few studies concerning how to maintain the stability of defects,which is important to ensure sustainable photocatalytic performance.Here,a novel strategy to modulate the structural properties of BiSbO_(4)using light-induced dynamic oxygen vacancies is reported by us for efficient and stable photocatalytic oxidation of formaldehyde.Interestingly,the continuous consumption and replenishment of vacancies(namely dynamic vacancies)ensure the dynamic stability of oxygen vacancies,thus guaranteeing the excellent photocatalytic stability.The oxygen vacancies could also accelerate the electron migration,inhibit the photogenerated electron/hole recombination,widen the light absorption spectra,and thus improve the photocatalytic formaldehyde removal performance.Combined with the results of in situ DRIFTS,the reaction mechanism for each step of formaldehyde oxidation is revealed.As supported by DFT calculation of Gibbs free energy,the introduction of oxygen vacancies into BiSbO_(4)can promote spontaneous process of formaldehyde oxidation.Our work highlights a promising approach for stabilizing the defects and proposes the photocatalytic reaction mechanism in combination with the thermodynamic functions.

A Pair-Electrosynthesis for Formate at Ultra-Low Voltage Via Coupling of CO_(2) Reduction and Formaldehyde Oxidation

Formate can be synthesized electrochemically by CO_(2) reduction reaction(CO_(2)RR)or formalde-hyde oxidation reaction(FOR).The CO_(2)RR approach suffers from kinetic-sluggish oxygen evolution reac-tion at the anode.To this end,an electrochemical sys-tem combining cathodic CO_(2)RR with anodic FOR was developed,which enables the formate electrosynthesis at ultra-low voltage.Cathodic CO_(2)RR employing the BiOCl electrode in H-cell exhibited formate Faradaic efficiency(FE)higher than 90% within a wide potential range from−0.48 to−1.32 V_(RHE).In flow cell,the current density of 100 mA cm^(−2) was achieved at−0.67 V_(RHE).The anodic FOR using the Cu_(2)O electrode displayed a low onset potential of−0.13 V_(RHE) and nearly 100%formate and H_(2) selectivity from 0.05 to 0.35 V_(RHE).The CO_(2)RR and FOR were constructed in a flow cell through membrane electrode assembly for the electrosynthesis of formate,where the CO_(2)RR//FOR delivered an enhanced current density of 100 mA cm^(−2) at 0.86 V.This work provides a promising pair-electrosynthesis of value-added chemicals with high FE and low energy consumption.

Polyoxymethylene dimethyl ethers synthesis from methanol and formaldehyde solution over one-pot synthesized spherical mesoporous sulfated zirconia

The synthesis of polyoxymethylene dimethyl ethers as an ideal diesel fuel additive is the current hot topic of modern petrochemical industry for their expedient properties in mitigating air pollutants emission during combustion.In this work,a series of spherical sulfated zirconia catalysts were prepared by a one-pot hydrothermal method assisted with surfactant cetyltrimethylammonium bromide(CTAB).The prepared sulfated zirconia catalysts were used to catalyze PODEn synthesis from methanol and formaldehyde solution.Various characterization(XRD,BET,SEM,TGA,NH_(3)-TPD,FTIR,and Py-IR)were employed to elaborate the structure–activity relationship of the studied catalytic system.The results demonstrated that S/Zr molar ratio in precursor solution played an effective role on catalyst morphology and acidic properties,where the weak Brønsted acid sites and strong Lewis acid sites were favorable to the conversion of methanol and formation of long-chain PODEn,respectively.The reaction parameters such as catalyst amount,molar ratio of FA/MeOH,reaction time,temperature and pressure were optimized.The speculated reaction pathway for PODEn synthesis was proposed based on the synergy of Brønsted and Lewis acid sites,which suggested that Brønsted and Lewis acid sites might be advantageous to the activation of polyoxymethylene hemiformals[CH_(3)(OCH_(2))_(n)OH]and methylene glycol(HOCH_(2)OH),respectively.

Kinetic Study of Curing Phenol-Formaldehyde/Tannin-Formaldehyde Composite Resins

This work presents a study on the uses of tannin-formadehyde derivative into phenolic resins. Eucalyptus tannins (T) were reacted with formaldehyde to form tannin-formaldehyde resin (TF). Then this derivative was used to prepare tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 %w/w. The kinetic values of thermal curing of Phenol-formaldehyde (PF), tannin-formaldehyde and tannin-formaldehyde/phenol-formaldehyde resins (TFPF) at 20 and 40 wt% from TF were studied by monitoring the weight changes which occurred in the samples weight during thermosetting process at four temperature (160°C, 180°C, 200°C and 220°C). The total evolved condensation products from curing reactions were about 32% - 36% per sample weight, and the rate of curing reaction constants was ranged between 0.163 %wt·min-1 at 160°C and 0.50 %wt·min-1 at 220°C. The path of TFPF curing and kinetic values indicated that these resins could be cured with the behavior and velocity comparable to that of PF. The activation energy of TFPF cross-linking was higher than that of PF. Increasing TF level to 20% and 40% into PF can reduce the amount of PF curing reactions density and weight loss percentage. The global kinetic properties showed that the TF participated in the thermoset network formation with acceptable activity and performance. The general results of this paper show that the TF is a suitable alternative material for partially replacement into PF resin.

含氮聚集诱导发光聚磷酸酯的一锅法合成及其荧光性能

非传统聚集诱导发光(AIE)聚合物,因不含苯环等芳香结构,具有较好的生物相容性和环境友好性,在细胞成像、生物医药等领域具有广阔的应用前景,但存在种类匮乏、量子产率低、荧光强度不足等问题,限制了其发展。为解决以上问题,以低毒、低腐蚀性的亚磷酸二甲酯及三异丙醇胺或三乙醇胺为原料,在无溶剂、无催化剂条件下,通过酯交换缩聚法,合成了含氮聚磷酸酯T1和T2。结果表明,所合成的含氮聚磷酸酯T1和T2在紫外光照射下均可发出明亮的蓝色荧光,其荧光强度随着浓度的升高而增强,具有显著的AIE特性,丰富了非传统AIE材料的种类。其中,T1分子结构中由于含有侧链甲基,在荧光强度、量子产率等方面均优于T2,为调节聚合物的荧光性能提供了一种新的方法。同时,研究发现,T1可以吸附空气中的甲醛,其吸附甲醛后颜色由无色变为粉色,且其荧光强度随吸附的甲醛浓度的增加而增强,有利于实现甲醛的荧光-比色双通道检测,为甲醛的灵敏检测提供了一种新的途径。

替硝唑合剂与甲醛甲酚联合封管治疗慢性牙髓炎的有效性及安全性分析

目的探讨替硝唑合剂与甲醛甲酚联合封管治疗慢性牙髓炎的有效性及安全性。方法选取2020年5月—2022年6月该院收治的80例慢性牙髓炎患者为研究对象,按照随机数字表法将其分为对照组和观察组,每组40例。两组均予以根管治疗,于此基础上对照组使用甲醛甲酚进行封管,观察组使用甲醛甲酚联合替硝唑合剂进行封管。比较两组临床疗效、咀嚼功能、炎症因子、不良反应发生情况。结果观察组治疗总有效率97.50%高于对照组的75.00%,差异有统计学意义(P<0.05)。治疗后,观察组的咬合力(143.02±8.97)lbs、咀嚼效率(88.05±6.14)%均高于对照组,组间差异有统计学意义(P<0.05)。治疗后,观察组C反应蛋白水平(9.14±2.67)mg/mL、白细胞介素水平(1.01±0.10)ng/mL、不良反应发生率5.00%均低于对照组,组间差异有统计学意义(P<0.05)。结论甲醛甲酚联合替硝唑合剂进行封管效果更佳,能促进咀嚼功能改善,降低炎症水平,降低不良反应发生率。

脲醛树脂类废弃建筑垃圾热解处理研究

脲醛树脂是一种优异的黏合剂,在建筑材料领域有着广泛的应用,传统的处理方式难以有效处置脲醛树脂类废弃建筑垃圾。创新性提出使用热解方法处理废旧脲醛树脂,通过热重-红外联用(TG-FTIR)系统分析脲醛树脂热解的反应行为与气相产物,为脲醛树脂热解处理提供理论依据和数据支撑。研究表明,脲醛树脂的热解主要分为水分及添加剂的挥发和树脂的裂解两个阶段,且主要以第2阶段为主;900℃时UF1(呈块状的脲醛树脂)的累计产气率比UF2(呈颗粒状的脲醛树脂)高32.6%,且随着温度从600℃提高到900℃,累计产气率提高不大;通过Coats-Redfern法确定了脲醛树脂热解的反应级数为1.4,UF1的活化能比UF2稍高;通过FTIR分析发现,脲醛树脂热解的气相产物主要是CO_(2),H_(2)O以及含有C—H键、N—H键、羰基的化合物,N元素主要以氮氢化合物而不是高污染的氮氧化合物形式存在。

氮掺杂对环境空气中TiO_(2)纳米催化剂抗甲醛光催化矿化的影响

通过氮掺杂TiO_(2)(N-TiO_(2))浸渍蜂窝过滤器构建了一系列原型光催化空气净化器(AP(N_(x)-C_(y)))系统,并用于在UV-LED光(1 W)照射条件下光催化分解0.5-5 ppm甲醛(CH_(2)O)蒸汽.在上述催化过滤器系统中,Nx和Cy分别代表N/Ti摩尔比(0-20)和N-TiO_(2)浓度(2-20 mg mL^(-1)).光催化分解实验结果表明,AP(N_(10)-C_(10))的性能最好,其催化CH2O转化为CO_(2)的转化率最高,循环反应10次后CO_(2)产率仍达到89.2%,在干燥空气中的清洁空气输送速率为9.45 L min^(-1).N10-C10的电荷载流子寿命(τa:1.70 ns)优于其他样品(如纯TiO_(2)的电荷载流子寿命为1.37 ns),这表明N缺陷(No)有助于降低带隙(3.10 eV)和产生氧空位OVs-Ti^(3+),这与密度泛函理论(DFT)模拟结果一致.采用原位漫反射红外傅里叶变换、电子顺磁共振和DFT分析等多种方法研究了CH_(2)O的光催化氧化途径.结果表明,氧化过程涉及多个能量有利的中间步骤(例如CH2O以CH_(2)O_(2)的形式在TiO_(2)-OV{110}表面的桥连O/OH基团上发生放热共价吸附,随后通过催化脱氢/氧化反应直接生成CO_(2):CH_(2)O_(2)/HCOO^(-)+•OH→H_(2)O+CO_(2)).这些步骤与具有N杂质的{101}表面上化学活性Ti原子的态密度计算结果一致.预计No缺陷和OVs的存在将通过降低活化能垒来影响反应能量和中间产物,从而在加湿条件下实现有效的矿化.综上,本文为设计和构建先进的光催化系统,并用于环境空气中醛类挥发性有机物(VOCs)的有效矿化提供了新思路.

乙醇醛合成及应用研究进展

乙醇醛作为重要的化工中间体,被广泛的应用于食品、医药卫生、化工等行业。综述了乙醇醛的合成工艺路线,包括以甲醛为原料通过氢甲酰化法,选择性醛糖反应,生物催化法;以乙二醇为原料通过化学氧化法、生物催化法等。其中近年来随着现代生物技术的发展,以乙二醇为原料经生物催化合成乙醇醛的方法具有良好的前景。

DFT Study of Oxygenated Organic Pollutants Catalyzed by Molybdenum Oxides: Comparison of Reaction Mechanisms of MoO_x + HCHO(x = 1, 2, 3)

The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms of MoOx(x = 1, 2, 3) catalyzing formaldehyde. Different products were obtained from three reactions. Of all three reactions, the barrier energy of Route ⅡA is the lowest(4.70 kcal/mol), which means in MoOx(x = 1, 2, 3), MoO2 has the best catalytic effect. Compared with other similar non-toxic treatments of formaldehyde, our barrier energy is the lowest. In this research, there was no good leaving group of the compound, so the mechanisms are addition reaction. We speculate that there must be an addition reaction to the more complex reactions to molybdenum oxides and aldehydes. As a chemical reagent for removing formaldehyde, it only absorbs formaldehyde and does not emit other toxic substances outward. Molybdenum oxides retain its original structures of the final products, which means it has excellent stability in the reaction of MoOx(x = 1, 2, 3) + HCHO. The mechanisms of all three reactions are addition reactions, but they are entirely different. As the number of oxygen atoms increases, the reaction mechanisms become simpler.

An Efficient Extraction-Free Method for Oxidative Desulfurization of Model Fuels Employing Cross-Linked Polyionic Liquid Phosphotungstate Catalysts

An efficient extraction-free oxidative desulfurization(ODS)process using a series of cross-linked polyionic liquid phosphotungstate(CLPIL-PW)catalysts is reported.The cross-linked PILs were prepared with DVB and 1-n-alkyl-3-vinyl imidazole hydrobromide(alkyl=ethyl,butyl,octyl,dodecyl),and were then assembled with phosphotungstic acid(H_(3)PW_(12)O_(40))to form the catalysts.The CLPIL-PWs have been applied to the oxidative removal of dibenzothiophene(DBT)from model oil with H_(2)O_(2) as an oxidant.The effects of ionic liquid(IL)cationic species,varying the DVB/IL molar ratio in the polymerization process,and varying operating conditions were investigated.The CLPIL-PWs were characterized by inductively coupled plasma(ICP)mass spectrometry,elemental analysis,scanning electron microscopy(SEM),Fourier transform infra-red(FTIR)spectroscopy,X-ray diffraction(XRD),^(13)C and^(31)P nuclear magnetic resonance(NMR)spectroscopy.The polydivinylbenzene-co-1-n-octyl-3-vinyl imidazole phosphotungstate(P(DVB-OVIm)PW)exhibited the highest DBT removal efficiency(99.9%)and remarkable recyclability,and could be reused eight times without reducing its activity.Finally,an extraction-free ODS mechanism is proposed.

Fe,N,S-doped porous carbon as oxygen reduction reaction catalyst in acidic medium with high activity and durability synthesized using CaCl_2 as template

Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.

Forward Looking Analysis Approach to Assess Copper Acetate Thermal Decomposition Reaction Mechanism

Thermal decomposition course of copper acetate monohydrate was monitored by combining diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) coupled with μ gas chromatography-mass spectrometry (μGC-MS) with other analytical techniques (thermogravimetry analysis and in situ X-ray diffraction). Non-isothermal kinetic was examined in air and Ar. A complete analysis of the evolution of infrared spectra matched with crystalline phase transition data during the course of reaction allows access to significant and accurate information about molecular dynamics. While thermogravimetry gives broad conclusion about two steps reaction (dehydration and decarboxylation), in line approach (in situ X-ray and in situ DRIFT coupled to μGC-MS) is proposed as an example of a new robust and forward-looking analysis. While decomposition mechanism of copper acetate monohydrate is still not well elucidated yet previously, the present in-line characterization results lead to accurate data making the corresponding mechanism explicit.

Synthesis and Properties of Polyurethane Elastomers Containing Sucrose as a Cross-Linker

Polyaddition using isocyanate and polyol forms polyurethane elastomer (PUE). However, this method has rarely been applied to the construction of PUEs containing sucrose. Hence, the introduction of sucrose (disaccharide) as a cross-linker via polyaddition remains a challenging subject in polymer chemistry. Here, we report the synthesis of PUEs using an aromatic isocyanate (4,4’-diphenylmethane diisocyanate), polyols including a polyether polyol (polytetramethylene glycol) and two polyester polyols (polycaprolactone and polycarbonate diols), and sucrose as a crosslinker by a one-shot method. The PUEs containing sucrose were successfully produced. The use of sucrose was essential to obtain the desired PUEs containing sucrose units in the main chain.