丙烯聚合N高效催化剂的研究 Ⅰ.丙烯聚合反应动力学

测定了N-催化剂体系丙烯常压淤浆聚合活性中心浓度(C_p)、链增长速度常数(k_p)、聚合物的分子量及其分布等参数,并与络合-Ⅱ型催化剂进行了比较。C_p用动力学外推法求取,分子量用凝胶渗透色谱法测定。结果表明,N-催化剂体系是一种长效体系,定向能力不受部分聚合条件变化的影响。与络合-Ⅱ型催化剂相比,该体系具有高活性的主要原因是其活性中心浓度较高。

丙烯聚合N高效催化剂的研究 Ⅱ.催化剂体系内外给电子体的作用

通过对聚合动力学曲线、催化剂活性、催化剂的定向能力、聚合物分子量、活性中心浓度(C_p)和链增长速度常数(K_p)等比较,研究了N-催化剂体系内外给电子体在催化丙烯聚合中的作用。结果表明,内给电子体可明显地改变聚合动力学曲线,外给电子体则无影响。内外给电子体均能提高催化活性和定向能力,但它们对C_p和K_p的影响却各不相同。

N-Ⅲ催化剂在间歇式液相本体法聚丙烯装置上的应用

本文介绍了丙烯聚合N-Ⅲ型高效载体催化剂在小本体聚丙烯装置上的应用情况,应用表明N—Ⅲ型催化剂具有高活性,抗原料中有害杂质能力强,聚合反应放热高峰平缓易控,氢调灵敏,产品质量好等特点,被广泛地应用于聚丙烯等化工原料的生产领域。

两钠装置尾气的低成本净化工艺及N-847D催化剂的应用

通过对两钠（通常指硝酸钠和亚硝酸钠）装置增加洗涤、再生流程以及对还原剂补给管线进行改造，净化流程相对稳定；采用高效选择性还原N-847D脱NOx （氮氧化物）催化剂，以气化氨或氨驰放气作为还原剂，在入口NOx含量为3700～4050 mg ／ Nm3、空速为2500～3500 h-1、反应床层为180～220℃、NH3／ NO≈0．75的条件下，两钠生产装置尾气净化后达标排放。

高活性低温脱硝催化剂在高浓度氮氧化物尾气超低排放治理工艺的应用

介绍了尾气净化工艺系统,在设计中利用喷雾除沫装置,清洗碱吸收尾气,同时预先将尾气与废热锅炉工艺气体进行热量交换,在既保证了净化效果的同时,又大大缩短了电加热器的使用时间,节省了电能,优化了整个稀硝酸、两钠生产装置工艺系统,降低了生产成本。

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO_2 Hydrogenation

Nitrogen-doped carbon nanotubes （NCNTs） were used as a support for iron （Fe） nanoparticles applied in car- bon dioxide （CO_2） hydrogenation at 633 K and 25 bar （1 bar = 10-5 Pa）. The Fe/NCNT catalyst promoted with both potassium （K） and manganese （Mn） showed high performance in CO_2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity （GHSV） of 3.1 L-（g·h）-1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promot- ed with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction （XRD）, temperature-programmed reduction （TPR） with molecular hydrogen （H2）, and in situ X-ray absorption near-edge structure （XANES） analysis. The Mn pro- moter stabilized wtistite （FeO） as an intermediate and lowered the TPR onset temperature. Catalytic ammo- nia （NH_3） decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

Mass Spectrometric Studies of Selective Oxidation of n-Butane over a Vanadium Phosphorus Oxide Catalyst

The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.

Synergistic effect of metallic nickel and cobalt oxides with nitrogen-doped carbon nanospheres for highly efficient oxygen evolution

The most energy-inefficient step in the oxygen evolution reaction(OER), which involves a complicated four-electron transfer process, limits the efficiency of the electrochemical water splitting. Here, well-defined Ni/Co3O4 nanoparticles coupled with N-doped carbon hybrids(Ni/Co3O4@NC) were synthesized via a facile impregnation-calcination method as efficient electrocatalysts for OER in alkaline media. Notably, the impregnation of the polymer with Ni and Co ions in the first step ensured the homogeneous distribution of metals, thus guaranteeing the subsequent in situ calcination reaction, which produced well-dispersed Ni and Co3O4 nanoparticles. Moreover, the N-doped carbon matrix formed at high temperatures could effectively prevent the aggregation and coalescence, and regulate the electronic configuration of active species. Benefiting from the synergistic effect between the Ni, Co3O4, and NC species, the obtained Ni/Co3O4@NC hybrids exhibited enhanced OER activities and remarkable stability in an alkaline solution with a smaller overpotential of 350 m V to afford 10 m A cm-2, lower Tafel slope of 52.27 m V dec-1, smaller charge-transfer resistance, and higher double-layer capacitance of 25.53 m F cm-2 compared to those of unary Co3O4@NC or Ni@NC metal hybrids. Therefore, this paper presents a facile strategy for designing other heteroatom-doped oxides coupled with ideal carbon materials as electrocatalysts for the OER.

Iron-incorporated nitrogen-doped carbon materials as oxygen reduction electrocatalysts for zinc-air batteries

The application of electrocatalysts for the oxygen reduction reaction(ORR) is vital in a variety of energy conversion technologies. Exploring low-cost ORR catalysts with high activity and long-term stability is highly desirable, although it still remains challenging. Herein, we report a facile and reliable route to convert ZIF-8 modified by Fe-phenanthroline into Fe-incorporated and N-doped carbon dodecahedron nanoarchitecture(Fe-NCDNA), in which carbon nanosheets are formed in situ as the building blocks with uniform Fe-N-C species decoration. Systematic electrochemical studies demonstrate that the as-synthesized Fe-NCDNA electrocatalyst possesses highly attractive catalytic features toward the ORR in terms of activity and durability in both alkaline and neutral media. The Zn-air battery with the optimal Fe-NCDNA catalyst as the cathode performs impressively, delivering a power density of 184 m W cm^–2 and a specific capacity of 801 m Ah g^–1;thus, it exhibits great competitive advantages over those of the Zn-air devices employing a Pt-based cathode electrocatalyst.

Trimethyl-1,4-Benzoquinone Synthesis via 2,3,6-Trimethylphenol Catalytic Oxidation by Oxygen in the Presence of Non-Keggin-Type Mo-V-Phosphoric Heteropoly Acid Solutions

In the present study, the modified （non-Keggin-type） aqueous solutions of Mo-V-phosphoric heteropoly acids HaPzMoyVx,Oh （HPA-x＇） were applied as homogeneous catalysts for the two-stage oxidation of TMP （2,3,6-trimethylphenol） by oxygen into TMQ （2,3,5-trimethyl-l,4-benzoquinone）, the latter being the key intermediate in the synthesis of vitamin E. The TMQ yield was analyzed regarding solvent type, reaction temperature, molar HPA-x ＇：TMP ratio, and the concentration of vanadium （V） in the HPA-x＇ solution. The TMQ yield was found to depend strongly on the catalyst redox potential and the rate of electron transfer. The results obtained enabled to establish the optimal reaction conditions as well as to suggest the reaction mechanism. In the target reaction, which proceeds in the two-phase system, the TMQ yield is higher than 99%. After phase separation, the catalyst is rapidly regenerated by oxygen and reused.

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.

Mg-doped SrTaO_(2)N as a visible-light-driven H_(2)-evolution photocatalyst for accelerated Z-scheme overall water splitting

Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.

Ag_3PO_4/Ag_2CO_3 p–n heterojunction composites with enhanced photocatalytic activity under visible light

Formation of a p–n heterojunction rather than p-type or n-type semiconductors can enhance the separation of photogenerated electrons and holes and increase the quantum efficiency of photocatalytic reactions owing to the difference of the electric potential in the inner electric field near the junction,pointing from n toward p. n-Ag3PO4/p-Ag2CO3 p–n heterojunction composites are prepared through a facile coprecipitation process. The obtained Ag3PO4/Ag2CO3 p–n heterojunctions exhibit excellent photocatalytic performance in the removal of rhodamine B（RhB） compared with Ag3PO4 and Ag2CO3. The 40%-Ag3PO4/Ag2CO3 composite photocatalyst（40 mol% Ag3PO4 and 60 mol% Ag2CO3） exhibits the best photocatalytic activity under visible light,demonstrating the ability to completely degrade RhB within 15 min. Transient photovoltage characterization and an active species trapping experiment further indicate that the formation of a p–n heterojunction structure can greatly enhance the separation efficiency of photogenerated carriers and produce more free h＋active species,which is the predominant contributor for RhB removal.

异丁基三乙氧基硅烷作为外给电子体生产高熔融指数聚丙烯

利用异丁基三乙氧基硅烷作为外给电子体与N-Ⅲ催化剂组成高活性及高氢调敏感性催化体系，在间歇式液相本体法聚丙烯生产工艺中，通过控制每釜氢气加入量为氢气钢瓶压降23-25MPa，单釜主催化剂加入量65g，生产熔融指数在30-35g／10min之间的高熔指聚丙烯，产品等规度97．0％，灰分1．3×10^-4。实验证明，异丁基三乙氧基硅烷作为外给电子体的N-Ⅲ催化体系反应初期活性适中，活性衰减慢，无明显放热高峰。

Bis(trifluoromethylsulfonyl)phenylamines as Internal Donors for Ziegler-Natta Polymerization Catalysts

Several bis（trifluoromethylsulfonyl）phenylamines have been synthesized and used as internal donors for the preparation of heterogeneous Ziegler-Natta catalysts for propylene polymerization. These new cata- lysts are highly active and stereospecific in combination with an external donor for the polymerization of propylene. The activity of these catalysts is dramatically influenced by the electronic capability of the phenyl substituents on the sulfonyl phenylamines. Therefore, the performances of the catalysts can be modified by adjusting the electronic property of the phenyl substituents of the sulfonyl phenylamines.

Cobalt-catalyzed redox-neutral synthesis of isoquinolines: C–H activation assisted by an oxidizing N–S bond

A redox‐neutral avenue to access isoquinolines has been realized by a Co（III）‐catalyzed C–H activa‐tion process. Starting from readily available N‐sulfinyl imine substrates and alkynes, the reaction occurred via N–S cleavage with broad substrate scope and functional group compatibility in the presence of cost‐effective cobalt catalysts.

Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3‐nitrostyrene over Co‐N‐C single‐atom catalyst in compressed CO_(2)

Single‐atom catalysts(SACs)have demonstrated excellent performances in chemoselective hydrogenation reactions.However,the employment of precious metals and/or organic solvents compromises their sustainability.Herein,we for the first time report the chemoselective hydrogenation of 3‐nitrostyrene over noble‐metal‐free Co‐N‐C SAC in green solvent—compressed CO2.An interesting inverted V‐curve relation is observed between the catalytic activity and CO2 pressure,where the conversion of 3‐nitrostyrene reaches the maximum of 100%at 5.0 MPa CO2(total pressure of 8.1 MPa).Meanwhile,the selectivities to 3‐vinylaniline at all pressures remain high(>99%).Phase behavior studies reveal that,in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa,bi‐phase composed of CO2/H_(2)gas‐rich phase and CO2‐expanded substrate liquid phase forms at total pressure of 8.1 MPa,which dramatically changes the reaction kinetics of the catalytic system.The reaction order with respect to H_(2)pressure decreases from~0.5 to zero at total pressure of 8.1 MPa,suggesting the dissolved CO2 in 3‐nitrostyrene greatly promotes the dissolution of H_(2)in the substrate,which is responsible for the high catalytic activity at the peak of the inverted V‐curve.

New frontiers of N-heterocyclic carbene catalysis

N-heterocyclic carbene （NHC） is both a family of strong o-donor ligands for transition metals and a privileged class of organocatalysts with synthetic potential that rivals popu- lar amine and phosphoric acid catalysts. NHC was found as a key catalytic species in thiamine diphosphate catalyzed biochemical reactions [1]. However, due to their inherent chemical instability, free NHCs had not been isolated until 1991 by Ardungo et al. [2]. Since then, the use of chiral NHC as a versatile organocatalyst has enjoyed tremendous advances and has helped to transform modem synthetic chemistry. There are over 2000 research papers dealing with both ＂N-heterocyclic carbene＂ and ＂Catalysis＂ in the past 15 years [3].

Recyclable bifunctional aluminum salen catalyst for CO2 fixation:the efficient formation of five-membered heterocyclic compounds

A variety of unique Al(salen) complexes functionalized by imidazolium-based ionic liquid(IL) moieties with the salen ligand at the two sides of 3,3′-position have been successfully prepared, rather than familiar 5,5′-position reported previously.The catalytic activity obtained by these bifunctional catalysts could be superior to those of the binary type catalysts in the formation of five-membered heterocyclic compounds from the cycloaddition reaction of CO_2 and three-membered heterocyclic compounds(including terminal epoxides and N-substituted aziridines), presumably due to the distinguished intramolecularly synergistic catalysis, which might lead to perform the cycloaddition reaction at ambient conditions and retain excellent yield and unprecedented chemo-or regioselectivity. Moreover, the polyether-based trifunctional Al(salen) catalysts with the best catalytic performance could be regenerated and reused at least eight times without any obvious decreases in catalytic activity. Finally,the kinetic investigation suggested the structure of catalysts had important influences on the catalytic activity, thereby proposing the possible reaction mechanism.

Novel Cu_3P/g-C_3N_4 p-n heterojunction photocatalysts for solar hydrogen generation

Developing efficient heterostructured photocatalysts to accelerate charge separation and transfer is crucial to improving photocatalytic hydrogen generation using solar energy. Herein, we report for the first time that p-type copper phosphide（Cu3P） coupled with n-type graphitic carbon nitride（g-C3N4） forms a p-n junction to accelerate charge separation and transfer for enhanced photocatalytic activity.The optimized Cu3P/g-C3N4 p-n heterojunction photocatalyst exhibits 95 times higher activity than bare g-C3N4, with an apparent quantum efficiency of 2.6% at 420 nm. A detail analysis of the reaction mechanism by photoluminescence,surface photovoltaics and electrochemical measurements revealed that the improved photocatalytic activity can be ascribed to efficient separation of photo-induced charge carriers. This work demonstrates that p-n junction structure is a useful strategy for developing efficient heterostructured photocatalysts.