Mars-van Krevelen-like Mechanism of CO Hydrogenation on an Iron Carbide Surface

Computational chemistry is used to explore a mechanism for CO hydrogenation to methane on iron carbides. As CO dissociation is endothermic on carbon terminated Fe₅C₂ (100) cuts, we explore a path starting with the hydrogenation of the surface, which liberates iron 4-fold sites for adsorption and dissociation of CO. The reaction cycle to methane resembles the Mars-van Krevelen mechanism for oxidation reactions.     

Catalysis of Selective Hydrogen/Deuterium Exchange at Allylic Positions Using Deuterium Oxide

Deuterated organic compounds can be prepared efficiently and cost effectively by the direct exchange of a hydrogen atom by a deuterium atom on a carbon center rather than classical synthetic procedures. H/D exchange is achieved at allylic positions of alkenes catalyzed by alkene isomerization catalyst 1. An outstanding degree of deuteration is achieved at positions accessible by isomerization in homogeneous and biphasic reaction settings.     

Theoretical Investigation of Hydrogen Adsorption and Dissociation on Iron and Iron Carbide Surfaces Using the ReaxFF Reactive Force Field Method

We have developed a ReaxFF reactive force field to describe hydrogen adsorption and dissociation on iron and iron carbide surfaces relevant for simulation of Fischer?CTropsch (FT) synthesis on iron catalysts. This force field enables large system (>>1000 atoms) simulations of hydrogen related reactions with iron. The ReaxFF force field parameters are trained against a substantial amount of structural and energetic data including the equations of state and heats of formation of iron and iron carbide related materials, as well as hydrogen interaction with iron surfaces and different phases of bulk iron. We have validated the accuracy and applicability of ReaxFF force field by carrying out molecular dynamics simulations of hydrogen adsorption, dissociation and recombination on iron and iron carbide surfaces. The barriers and reaction energies for molecular dissociation on these two types of surfaces have been compared and the effect of subsurface carbon on hydrogen interaction with iron surface is evaluated. We found that existence of carbon atoms at subsurface iron sites tends to increase the hydrogen dissociation energy barrier on the surface, and also makes the corresponding hydrogen dissociative state relatively more stable compared to that on bare iron. These properties of iron carbide will affect the dissociation rate of H₂ and will retain more surface hydride species, thus influencing the dynamics of the FT synthesis process.     

超声处理对活性炭表面形态及负载催化剂活性的影响

采用超声预处理活性炭,并用N_2物理吸附、X射线能谱仪(EDS)、透射电镜(TEM)、和场发射扫描电镜(FE-SEM)等表征手段,研究了超声预处理条件对活性炭表面结构、化学成分及表面形貌以及所负载钌基氨合成催化剂性能的影响。研究结果表明,超声预处理活性炭,可有效降低活性炭表面灰分和不稳定含氧基团的含量,从而提高所负载催化剂的活性。在实验范围内,当超声频率为39.0 kHz,功率为100w时,在10 000 h~(-1),10.0 MPa和400℃的反应条件下,钌基催化剂的反应速率达到了97.6 mmol/(g·h)。     

合成2,3,5-三甲酚催化剂的研究

采用等体积浸渍法制备负载型催化剂用于3,5-二甲酚甲基化反应,在固定床反应器中考察了载体的焙烧温度、助剂、催化剂的焙烧温度和焙烧时间等因素对催化剂活性影响分析。结果表明:Fe2O3-Cr2O3/Al2O3催化剂在反应中具有较高的反应活性和选择性。     

锆/铪基催化剂催化转移加氢反应的研究进展

催化转化是可再生生物质资源利用的重要途径,高效催化剂的构建是生物质及其衍生物催化转化的关键环节.生物质衍生羰基类化合物加氢转化为醇或酯类化合物是生物质催化转化利用过程中重要的反应步骤.由于氢转移加氢反应过程具有反应条件温和的优点,因此非均相氢转移加氢催化剂在羰基类生物质平台分子转化中得到广泛应用.过渡金属锆、铪是常用的...     

Effect of Hydrogen Treatment on the Catalytic Activity of Iron Oxide Based Materials Dispersed Over Activated Carbon: Investigations Toward Hydrogen Peroxide Decomposition

The effect of hydrogen treatment (400 °C/1 h) on the catalytic properties toward H₂O₂ decomposition of iron oxide based materials dispersed over activated carbon were investigated. Two different supports were evaluated: a commercial activated carbon (ACM) and an activated carbon produced from spent coffee grounds (ACR). The catalysts were characterized using XRD, SEM, N₂-sorption, XPS and TPR analysis. The main results suggest the formation of composites with high surface area (>800 m² g^?1) and the hydrogen treatment resulted in a great increase in the catalytic activity, probably as a function of the reduced iron species (Fe²⁺ and Fe⁰) formed with the treatment. Moreover, the catalyst prepared with ACR showed to be more active than that prepared from ACM.     

饱和活性炭催化双氧水氧化处理染料废水生化出水

分别采用Fe~(2+)/H_2O_2、活性炭(AC)/H_2O_2、AC/H_2O_2/Fe~(2+)和再生AC四种体系对染料废水生化出水进行处理,分别考察了不同体系中,H_2O_2的投加浓度、n(H_2O_2)/n(Fe~(2+))、pH和反应时间及再生炭对废水处理效果的影响,并对处理效果进行对比。结果表明AC/H_2O_2/Fe~(2+)体系对废水COD的去除效果最好,去除率为64%,再生AC对废水色度去除率最高为94%。     

Active and Recyclable Polyethylene‐Supported Iridium‐(N‐ Heterocyclic Carbene) Catalyst for Hydrogen/Deuterium Exchange Reactions

The multistep synthesis of a polyethylene‐supported iridium(III)‐(N‐heterocyclic carbene) hydrogen/deuterium exchange catalyst was performed starting from an iodo‐polyethylene obtained via catalyzed polyethylene chain growth (CCG) on magnesium. Unique thermomorphic polyethylene properties give the possibility to perform catalytic hydrogen/deuterium exchange reactions at 100 °C in the homogeneous phase with simple catalyst separation as a precipitate at room temperature. The catalytic activity of the polymer‐supported catalyst was compared with that of its monomeric analogue. The catalytic studies showed that the supported catalyst exhibits similar profiles and turnover numbers as homogeneous counterparts without deactivation.

     

Low-Temperature Adsorption of Hydrogen on Activated Carbon

Abstract

The adsorption isotherm of pure hydrogen on activated carbon (coconut shell) was determined at — 186[ddot]C over a pressure range of 1 to 772 mm Hg. A McBain balance apparatus with a modified refrigerant thermostat was used.     

活性炭改性对松香歧化用Pd/C催化剂性能的影响

采用沉积-沉淀法制备了4% Pd/C催化剂（Pd质量分数4%）,分别以硝酸、盐酸、双氧水和氨水4种溶剂对Pd/C的载体活性炭进行改性,并对载体活性炭的比表面积和孔结构、零电荷点（PZC）以及活性组分Pd的分散度进行了表征,研究了活性炭改性对Pd催化剂在松香歧化反应中催化性能的影响。结果表明：经氨水改性后活性炭比表面积孔径增大且活性炭PZC值升高,有利于活性组分Pd在载体表面的分散,以氨水改性活性炭为载体制备得到的Pd/C催化剂活性最高,在催化剂投料量为0.03%,280℃反应2 h条件下,脱氢枞酸质量分数高达81.7%。     

Characterization of the N370S Mutant of Glucocerebrosidase by Hydrogen/Deuterium Exchange Mass Spectrometry

An asparagine‐to‐serine substitution at residue 370 (N370S) in glucocerebrosidase (GCase) is the most prevalent mutation leading to Gaucher's disease, the most common lysosomal storage disorder. Two types of hydrogen/deuterium exchange experiment coupled with proteolysis and liquid chromatography–mass spectrometry (HDX–MS) were used to investigate the dynamic properties and unfolding stability of wt, R495H, and N370S GCases in the presence and absence of ligands. R495H GCase is used for enzyme replacement therapy and is considered to be a wt surrogate, whereas N370S is the most prevalent mutation leading to Gaucher's disease. Time‐course HDX experiments of the GCases were performed under near‐physiological conditions to detect the protein's local unfolding motions at a submolecular level. In guanidine‐titration experiments, HDX reactions were performed with various concentrations of a chemical denaturant to provide the global stability of the proteins. The two types of experiment showed that all three purified GCases, wt, R495H, and N370S, have virtually identical local unfolding motions and global stabilities in solution. Combined with previous X‐ray crystallographic studies, which showed indistinguishable backbone conformations for N370S and R495H GCase mutants and very similar melting temperatures for the wt, R495H, and N370S mutants, all three GCases are likely to have virtually identical structural and dynamic properties in solution. The guanidine‐titration experiments revealed that the pharmacological chaperone, isofagomine (IFG), interacts more weakly with the N370S mutant than with the R495H GCase; this is consistent with the higher IC₅₀ value of IFG against N370S than against R495H. The time‐course experiments showed that IFG restricts the local unfolding motions of N370S in the same way as those of R495H when the ligand saturates the proteins.     

功能化活性炭固载离子液体催化剂

制备了活性炭固载溴化1-（2-胺乙基氢溴酸）-3-甲基咪唑翁盐离子液体催化剂,并用TG和XPS对催化剂进行了表征。将该催化剂首次用于Knoevenagel缩合反应,结果表明活性炭固载离子液体催化剂具有良好的催化活性和稳定性,同时克服了均相催化剂难以分离的不足。     

负载型钌炭加氢催化剂的工艺研究

通过对负载型钌炭催化剂的制备工艺的研究,分析讨论了载体种类、制备工艺中的负载和还原操作对钌炭催化剂性能的影响。研究结果表明:在催化剂的制备过程中,活性炭载体、负载方式和还原操作对表面活性金属的分散度有影响,从而造成催化剂的性能差异。选择椰壳炭为载体、沉淀法进行活性金属的负载,经过液相法硼氢化钠还原得到的催化剂表面活性金属的分散度高,催化剂在苯部分加氢反应中具有高活性和高选择性,环己烯的收率达到55%。     

铁矿石孔隙度对其还原和碳化铁生成的影响

在1023 K温度下用热重法结合XRD和EDX分析研究了70%H2-30%CH4混合气体还原铁矿石制备碳化铁的过程,测定了原矿和还原中间产物的微孔分布. 结果表明,相同反应条件下微观结构不同的铁矿石其还原速率和碳化速率有较大差别,巴西块矿、澳大利亚块矿及南非球团矿在50 min内都可以全部还原,此后生成碳化铁;而南非块矿则需90 min才能基本还原,此后没有碳化铁生成. 疏松多孔的铁矿石较致密铁矿石的还原速率快,生成的还原铁结构疏松,有利于碳化反应的进行. 铁矿石还原后,0.5~3.5 nm微孔孔容积率约提高2倍,分布规律与原矿石相似,3.5~13 nm的微孔孔容积提高显著,这些对还原速率和碳化铁的生成反应有较大影响.     

高温氢气处理对活性炭及钯炭催化剂性能的影响

采用高温氢气对不同活性炭进行处理,并分别采用比表面分析仪(BET)、红外光谱(IR)、氩气-程序升温脱附实验(Ar-TPD)和热重分析(TGA)对高温氢气处理前后的活性炭进行表征.结果表明,高温氢气处理对活性炭的孔结构和比表面影响较小,高温氢气处理后活性炭表面含氧官能团含量降低.以高温氢气处理后的活性炭为载体制备钯炭催化剂,催化剂上的钯的分散度降低,在粗对苯二甲酸精制反应中的初活性下降.     

载体处理对Pt/C催化剂的选择性加氢性能影响

研究了活性炭处理方式对以其为载体制备的铂炭催化剂性能的影响,以对氯硝基苯催化加氢制备对氯苯胺反应为模型反应对催化剂的性能进行评价。结果表明,经过处理的活性炭制备的铂炭在对氯硝基苯加氢反应中表现出的催化性能更高,5%NaOH在80℃下处理2 h的活性炭可以达到最佳效果,所制备的Pt/C催化剂重复使用4次,对氯苯胺收率在99%以上,脱氯率在0.3%以下。     

原料气氢氮分压变化对熔铁催化剂氨合成率的影响

通过理论分析和实验,提出了在工业条件下原料气中氢氮分压变化（包括氢氮比、惰性气体含量、合成压力变化）与熔铁催化剂氨合成率变化之间的关系式。利用该式所得的计算值与实验值十分吻合。     

Advanced Surface of Fibrous Activated Carbon Immobilized with FeO/TiO2 for Photocatalytic Evolution of Hydrogen under Visible Light

FeO-doped TiO₂ nanoparticle photocatalysts were immobilized onto the surface of fibrous activated carbon (ACF) via a sol-gel process. As an adsorbent and photocatalyst, FeO-TiO₂ on immobilized ACFs (FeO-TiO₂/ACF) greatly improved the photocatalysis rate of hydrogen production as compared with pure TiO₂ and ACF-TiO₂ under UV irradiation and visible light. The addition of ACFs surface significantly reduced the photogenerated pairs of electrons-hole recombination, thereby promoting the photocatalysis action of doped photo-metal oxides of FeO-TiO₂. Co-doping of FeO onto the lattice of the TiO₂ approach can improve the absorption activity of visible light through photo-metal oxide of TiO₂ and further enhance hydrogen production under visible light. The photocatalytic fabrics (FeO-TiO₂/ACF) were effortlessly split out from the experimental solution for re-utilization and exhibited high stability even after five complete regeneration cycles.     

Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide Mediated by the Carbonylchlorohydrido‐ tris(triphenylphosphine)ruthenium(II) Complex

The catalytic properties of several ruthenium, osmium and rhodium hydride complexes for hydrogen/deuterium (H/D) exchange between olefins and deuterium oxide (D₂O) were investigated. The most effective catalytic precursor was found to be the carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) complex. Through H/D exchange between metal hydride and D₂O, and reversible olefin insertion into an Ru H(D) bond, protons attached to olefinic carbons and alkyl chains of olefins can all undergo H/D exchange with D₂O. The catalytic reactions can be used to deuterate both terminal and internal olefins, for example, styrene, stilbene and cyclooctene.