X-射线吸收谱原位表征Cu-Zn/SiO2催化剂Cu价态

铜基催化剂的价态组成与制备方法、还原温度有关,也是决定其催化性能的关键因素.本文对比研究Cu-Zn/SiO₂和Cu/SiO₂催化剂前驱体在不同还原温度下的价态组成及其醋酸甲酯加氢性能.采用同步辐射X射线吸收谱原位表征催化剂前驱体的Cu K边的X射线近边吸收谱（XANES）,通过线性组合分析方法（LCF）拟合XANES吸收谱得到了催化剂前驱体在不同还原温度下氧化态（Cu²⁺、Cu⁺）和金属态（Cu⁰）的组分含量.结果表明：（1）采用蒸氨法添加Zn制备的Cu-Zn/SiO₂催化剂前驱体铜组分还原度高;（2）催化剂前驱体在还原过程中Cu⁺主要存在于低温还原阶段（<250℃）,且Cu⁰+Cu⁺含量较低（≤ 40%）;（3）金属态铜是醋酸酯加氢反应的活性中心.     

Cu+/SiO2-ZrO2催化剂的制备及其催化甲醇氧化羰基化性能

采用溶胶-凝胶法制备了SiO₂-ZrO₂复合氧化物载体,通过和CuCl₂进行离子交换制备了Cu⁺/SiO₂-ZrO₂催化剂,并研究其催化甲醇液相氧化羰基化合成碳酸二甲酯性能。结果表明,Zr以离子形式进入无定型SiO₂骨架结构中形成Si－O－Zr键,同时产生较强的B酸中心。CuCl₂通过热处理自还原为CuCl分散在SiO₂-ZrO₂载体表面,并与载体表面B酸发生离子交换形成Cu⁺物种,从而保留了活性金属组分Cu,脱除大部分的Cl元素,改善催化剂失活和设备腐蚀等问题。当焙烧温度为450℃时,催化剂表现出良好的催化活性,CH₃OH转化率、DMC选择性和时空收率分别达到10.0%、79.4%和1.45g/(g·h)。
     

催化剂表面Cu0含量对二氧化碳加氢合成C2+醇性能的影响

通过在空气气氛下焙烧Cu@Fe-MIL-88B MOF材料制备了CuFe组分均匀分散的催化剂前驱物, 该前驱物经过不同温度下的预还原制得表面具有不同Cu和Fe价态分布的系列催化剂. 将所制备的催化剂用于固定床反应器上CO₂加氢合成C₂₊醇的性能研究, 并结合催化剂的X射线衍射(XRD)、 X射线光电子能谱(XPS)、 氢气程序升温还原(H₂-TPR)、 氮气吸附-脱附、 扫描电子显微镜(SEM) 和高分辨率透射电子显微镜(HRTEM)等表征结果发现, 较高的还原温度增加了催化剂表面低价态的Cu和Fe的含量; 当还原温度为350 ℃时, 催化剂表面Cu⁰/(Cu⁺+Cu⁰)摩尔比为73.9%, 单质Fe摩尔分数为0.40%, 催化效果最好, CO₂转化率达到6.82%, 总醇选择性为39.4%, 其中C₂₊醇的摩尔比达到95.1%.     

铈改性的铜/六方介孔二氧化硅催化剂在温和反应条件下高效地将草酸二甲酯氢化为乙二醇（英文）

采用蒸氨法制备了一种高效的铈改性铜/六方介孔二氧化硅(xCe-Cu/HMS)催化剂，用于草酸二甲酯(DMO)气相化学选择性氢化成乙二醇(EG)。铈助剂可以显著提高催化剂的性能，在引入1.2%的铈后，催化剂的性能最好。在温和的条件下(200℃，2.0MPa, H₂/DMO=100, LHSVDMO=1.2h^-1), DMO转化率和EG选择性分别达到了99.6%和96.3%。表征结果显示，Ce修饰的Cu/HMS可以增强Cu与载体之间的相互作用，改善Cu的分散性，并保持适当的Cu⁺/(Cu⁺+Cu⁰)的比例。本研究采用简单、低成本的路线，合成了具有优良催化性能的Ce改性的Cu-HMS催化剂，实现了在温和的条件下DMO向EG的高选择性转化。     

同晶取代法制备Cu-Ni双金属催化剂及其催化CO加氢合成乙醇性能

采用定向同晶取代法制备了一系列镍孔雀石前驱体的Cu-Ni双金属催化剂。考察了前驱体结构以及催化剂表面组成对催化剂催化性能的影响,并采用浆态床反应器对催化剂的CO加氢制乙醇性能进行评价。实验结果表明,采用定向同晶取代法可以制备出（Cu,Ni）₂CO₃（OH）₂纯物相,取代后的Ni²⁺主要富集在前驱体（Cu,Ni）₂CO₃（OH）₂表面。焙烧后形成的（Cu_x,Ni_1-x）O固溶体均匀地分散在CuO晶体结构中。还原后的催化剂中Cu、Ni相互均匀分散形成活性界面,促进了低碳醇的合成。其中,不连续分布的Ni活性位点阻止了碳链的进一步增长,从而提高了乙醇选择性。当Ni/Cu原料比为45：100时,（Cu_x,Ni_1-x）O固溶体与CuO之间有较强的相互作用,表现出最好的反应活性和乙醇选择性。     

在仲丁醇脱氢反应中负载型铜催化剂的研究

采用浸渍法制备Cu/SiO₂和Cu-ZnO/SiO₂催化剂.研究了活性物种Cu和助剂ZnO的担载量对催化剂的结构和性能的影响,同时考察该催化剂对仲丁醇脱氢活性和选择性的影响.借助XRD和TPR对催化剂进行了表征,结果表明,高分散的Cu⁰为反应的活性中心,ZnO起到分散和稳定铜物种的作用.铜-锌之间的某种相互作用导致了缩合产物增加.     

Ce金属改性对Cu-SAPO-34催化剂水热稳定性能的影响

采用浸渍法制备系列铜铈复合氧化物分子筛催化剂（Cu-Ce/SAPO-34）,探讨了Ce负载量对Cu/SAPO-34催化剂的水热稳定性的影响,通过XRD、SEM、H₂-TPR、XPS和NH₃-TPD等表征手段分析不同催化剂活性和稳定性差异的原因。研究表明,750℃水热老化未造成Cu-Ce/SAPO-34催化剂菱沸石（chabazite,CHA）骨架坍塌,但破坏了部分孔结构和酸性位点,使催化剂表面结晶度下降。水热老化促使催化剂晶格发生拉伸畸变,使Cu²⁺迁移到催化剂表面,Cu²⁺和Ce⁴⁺团簇形成CuO和CeO₂,造成催化剂的Cu活性物种减少和氧空穴浓度降低,所以Cu-Ce/SAPO-34的NH₃选择性催化还原（NH₃-Selective Catalytic Reduction,NH₃-SCR）性能下降。掺杂Ce能提高Cu/SAPO-34催化剂表面的Cu²⁺和Cu⁺活性物种量,减少Cu物种团簇形成CuO,改善催化剂表面活性Cu物种分布性。提高Ce的负载量能稳固Cu-Ce/SAPO-34催化剂的结构,使中、弱强度酸位点得以维持,从而提高其水热稳定性。结果表明,在研究的系列Cu-Ce/SAPO-34催化剂中,Cu/Ce质量比为4：5时具有最佳的水热稳定性。     

具有高离子识别能力的镉离子表面印迹材料的制备及其离子识别机理的研究

采用氨基-过硫酸盐氧化还原引发体系, 先实现了甲基丙烯酸羟乙酯(HEMA)在微米级硅胶微粒表面的引发接枝聚合, 制得高接枝度的接枝微粒PHEMA/SiO₂. 然后使接枝大分子PHEMA的侧羟基与5-氯-8-羟基喹啉(CHQ)发生亲核取代反应, 将8-羟基喹啉(HQ)基团键合在接枝大分子侧链, 使接枝大分子PHEMA实现8-羟基喹啉功能化转变, 制得表面含有高密度HQ基团的功能接枝微粒HQ-PHEMA/SiO₂, 考察研究了功能微粒HQ-PHEMA/SiO₂对Cd²⁺离子的强螯合吸附作用. 在此基础上, 采用本课题组建立的新的分子表面印迹技术, 以Cd²⁺离子为模板离子, 二氯乙醚为交联剂, 对接枝在硅胶表面的功能大分子链HQ-PHEMA进行了离子印迹, 制备了Cd²⁺离子表面印迹材料IIP-HQP/SiO₂, 深入考察研究了其离子识别与结合特性. 实验结果表明, 该离子表面印迹材料对Cd²⁺离子具有特异的识别选择性与优良的结合亲和性, 相对于Cu²⁺和Pb²⁺两种对比离子, 印迹材料IIP-HQP/SiO₂对Cd²⁺离子的识别选择性系数分别高达25.52和22.91, 显示出超高的离子识别能力.     

TiOx/SiO2复合载体上高分散Au催化剂的CO氧化性能

负载型Au催化剂中金与载体间存在相互作用,载体性质能够影响Au纳米颗粒分散度及稳定性.本文通过表面溶胶-凝胶(SSG)法制备了TiO_x/SiO₂复合载体,以期增加氧化物载体表面配位不饱和度从而使其具有较高的金属分散性,并利用低能离子散射(LEIS)谱、X射线光电子能谱(XPS)、X射线衍射(XRD)、透射电子显微镜(TEM)及N₂物理吸附(BET)等手段对载体及催化剂进行表征分析.实验表明TiO_x/SiO₂复合载体表面TiO_x分散性良好,没有形成明显的TiO₂晶相,且与SiO₂间形成Ti―O―Si键.与Au/TiO₂相比, Au/TiO_x/SiO₂催化剂中Au纳米颗粒的分散性更好,因而CO氧化活性显著提高. TiO_x/SiO₂复合载体上的TiO₂膜是Au的主要表面键合位,导致Au与载体间相互作用增强,从而使得Au纳米颗粒抗烧结能力提高,同时催化剂反应稳定性得到改善.     

Ce改性对CuLDH催化CO2加氢制甲醇性能的影响

通过向CuMgAl水滑石(CuLDH)催化剂中添加不同量的Ce,合成了一系列Ce改性的CuLDH-Cex催化剂。采用X射线衍射(XRD)、N₂吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)等分析手段对催化剂的理化性质进行表征。结果表明,添加Ce会改变Cu-LDH催化剂的水滑石结构,适量的Ce会增大催化剂的比表面积,改善了Cu颗粒的分散度。同时,适量的Ce有利于增加催化剂表面强碱性位点的密度和氧空位的数量,促进了CO₂的吸附和转化。Ce有利于调变催化剂表面的Cu⁺/Cu⁰比例,较高的Cu⁺/Cu⁰比例有利于甲醇的生成。当Ce/Cu比例为0.3时,在空速为9000 mL/(g·h),温度为240℃,压力为2.5 MPa的条件下,催化剂的CO₂的转化率为7.5%,甲醇选择性为78.4%,甲醇的时空收率最高可达362.8 g/(kg·h)。通过原位红外光谱(in-situ DRIFTS)证明CuLDH-Ce0.3催...     

Urchin-like CoCu Bimetallic Nanocomposites for Catalytic Hydrogenolysis of Glycerol to Propanediols

Bimetallic CoCu nanocomposites were synthesized in polyol by using Ru as heterogeneous nucleation agent and stearic acid as surfactant, and their catalytic properties were investi- gated by hydrogenolysis of glycerol to propanediols. It was found that the surfactant could induce Co nanocrystals to form nanowires as structure-directing agent, while it's ineffective for Cu because only spherical Cu particles were produced under the same condition. When Co²⁺ and Cu²⁺ coexist in polyol, Cu²⁺ is firstly reduced and forms the spherical particles, and then the Cu particles afford surface for the subsequential reduction of Co²⁺ and growth of Co nanocrystals to form the nanorods, obtaining the urchin-like CoCu nanocomposites. The catalytic performance in selective hydrogenolysis of glycerol to propanediols proposed that the CoCu urchin-like nanocomposites was superior to the Co nanowires possibly due to that the synergistic effect between Co and Cu component promoted conversion of glyc-erol and obtained the higher propanediol yields based on the specific surface areas of the catalysts.     

Na促进的CuCoMn催化剂催化生物质合成气合成高醇

研究钠促进的CuCoMn催化剂的特性及其在生物质气化合成气合成高醇中的应用. 研究了催化剂中Na含量及合成条件(温度、压力和空速)对生物质基合成气合成高醇性能的影响. 发现CuCoMnNa_0.1催化剂较适合高醇合成, 在300 °C以下, 随着温度的上升, 碳转化率增大, 而醇选择性降低. 压力的增加有利于醇的合成, 增大空速会明显降低碳转化率, 但醇时空产率则因转换频率的增加而增大. 在所考察的范围内, 醇产率最高达到304.6 g·kg^-1·h^-1, 其中C₂₊高醇(C₂-C₆醇)占64.4% (w, 质量分数). 醇产物和烃产物均符合ASF (Anderson- Schulz-Flory)分布关系. 根据催化剂性能与表征分析, Na的加入有利于提高生物质气化合成气合成高醇的选择性和活性元素Cu、Co的分散性. X射线光电子谱(XPS)测试结果显示反应后的催化剂表面上, Cu以Cu⁺和Cu⁰的混合形式存在, 而Co则是Co²⁺/Co³⁺和Co⁰的混合物. 增加Na的含量, Cu⁰/Cu⁺比率和Co⁰的强度均随之减小.     

Cu-LaCoO3催化剂选择氢解生物质基糠醇制备1,5-和1,2-戊二醇

高效转化可再生生物质资源制备人类社会必需的燃料和化学品是当前关注和研究的热点之一.生物质基糠醇来源于玉米芯、甘蔗渣、秸秆等农林副产物,价廉易得,是选择氢解合成高附加值1,2-和1,5-戊二醇的理想原料.目前生物质基呋喃衍生物氢解制备二元醇的研究主要集中在Pt,Ru,Rh和Ir等贵金属催化剂,对无Cr非贵金属催化剂的研究甚少.基于纳米Cu催化剂较高的C-O键氢解活性和较低的C-C键裂解活性,以及碱性载体对反应物和反应中间体的稳定作用,我们在前期Cu-Mg3AlO4.5和Cu-Al2O3催化剂催化糠醇氢解研究基础上,以具有一定碱性的ABO3结构的钙钛矿型化合物为载体负载活性Cu开展糠醇氢解研究,深入研究催化剂结构、组成和活性金属价态等对催化剂活性和选择性影响,并研究了催化剂循环使用稳定性.首先我们采用柠檬酸一步络合法制备了一系列具有一定钙钛矿结构的不同Cu负载量(0-20 wt％)的Cu-LaCoO3催化剂以及LaCoO3负载的5 wt％Pt,Ru,Rh和Pd催化剂并考察了它们的糠醇选择氢解制备戊二醇性能.研究发现,在相同活性金属负载量(5 wt％)时,Cu-LaCoO3催化剂具有较优异的呋喃环C-O键氢解活性,而贵金属催化剂倾向于催化呋喃环C=C键加氢饱和.考察不同Cu负载量的Cu-LaCoO3催化剂催化糠醇氢解性能发现,随着Cu负载量的增加,糠醇转化率先升高后降低,在10 wt％Cu负载量时达最高(94.6％),戊二醇总选择性也随Cu负载量的增加先升高后降低,在5 wt％Cu负载量时最高(52.2％),总体以10 wt％Cu负载量催化剂表现出最优异的性能.接着我们考察了反应动力学条件如温度、压力和反应时间以及还原处理条件对10 wt％Cu-LaCoO3催化性能的影响.研究发现适当的高温(～433 K)和高压(6 MPa H2)有利于Cu-LaCoO3催化糠醇氢解制戊二醇,而低浓度氢气(5 vol％)还原有利于1,5-戊二醇的生成,高氢气浓度(纯氢)还原有利于呋喃环加氢饱和的四氢糠醇生成.10 wt％Cu负载量的催化剂经5％H2-95％N2处理后,在413 K和6 MPa H2条件下可取得100％的糠醇转化率以及55.5％的戊二醇总选择性(其中1,5-戊二醇和1,2-戊二醇的选择性之比接近3:1).进一步考察了10 wt％Cu-LaCoO3催化剂的循环使用稳定性,研究发现无论是在高初始转化率(～93.7％)还是低初始转化率(～30.5％)条件下,经多次循环使用后糠醇转化率先升高后基本保持不变,而戊二醇总选择性呈下降趋势,四氢糠醇的选择性逐渐上升.结合XRD,XPS,BET,H2-TPR,CO2-TPD,NH3-TPD和HRTEM等多种表征技术对Cu-LaCoO3催化剂的结构及在糠醇氢解反应中的活性位进行了表征,发现高分散的活性物种、合适的碱性以及部分还原的活性组分均有利于提高催化剂的活性与1,5-戊二醇的化学选择性,高分散的Cu0与部分还原的Co3O4(很可能是CoO)之间的协同催化对于取得较优异的糠醇氢解性能,尤其是较高的1,5-/1,2-戊二醇比例至关重要.     

Metal sulfates-catalyzed butanolysis of cellulose: butyl levulinate production and optimization

Direct production of butyl levulinate (BL) by butanolysis of cellulose was carried out using single or combined metal sulfates catalysts. The synergetic enhancement of the ferric sulfate and aluminum sulfate can improve the conversion of cellulose to BL. Moreover, the butanolysis of cellulose was optimized by using response surface methodology. Under the optimum conditions of 194 °C, catalyst concentration 10.0 g/L and reaction time 3 h, the average cellulose conversion of 100% and BL yield of 40.3% were obtained. In addition, the analysis of liquid products and the characterization of catalyst were performed, and the reusability experiments showed that the metal sulfates can be easily recycled and be reused more than five times with high activity in the butanolysis process. This study provided an economical and feasible method for bio-based BL production from cellulose.     

Furfural and 5-Hydroxymethylfurfural Production from Sugar Mixture Using Deep Eutectic Solvent/MIBK System

Choline chloride (ChCl) / glycolic acid (GA) deep eutectic solvent (DES) media with high water content but without any additional catalyst are introduced in furfural and 5-hydroxymethylfurfural (HMF) production. The effects of water content, reaction time, and reaction temperature are investigated with two feedstocks: a glucose/xylose mixture and birch sawdust. Based on the results, 10 equivalent quantities of water (32.9 wt.%) were revealed to be beneficial for conversions without rupturing the DES structure. The optimal reaction conditions were 160 °C and 10 minutes for the sugar mixture and 170 °C and 10 minutes for birch sawdust in a microwave reactor. High furfural yields were achieved, namely 62 % from the sugar mixture and 37.5 % from birch sawdust. HMF yields were low, but since the characterization of the solid residue of sawdust, after DES treatment, was revealed to contain only cellulose (49 %) and lignin (52 %), the treatment could be potentially utilized in a biorefinery concept where the main products are obtained from the cellulose fraction. Extraction of products into the organic phase (methyl isobutyl ketone, MIBK) during the reaction enabled the recycling of the DES phase, and yields remained high for three runs of recycling.     

Effect of Physicochemical Characteristics of Cellulosic Substrates on Enzymatic Hydrolysis by Means of a Multi-Stage Process for Cellobiose Production

The effect of two types of cellulose, microcrystalline cellulose and paper pulp, on enzymatic hydrolysis for cellobiose production was investigated. The particle size, the relative crystallinity index and the water retention value were determined for both celluloses. A previously studied multistage hydrolysis process that proved to enhance the cellobiose production was studied with both types of celluloses. The cellobiose yield exhibited a significant improvement (120% for the microcrystalline cellulose and 75% for the paper pulp) with the multistage hydrolysis process compared to continuous hydrolysis. The conversion of cellulose to cellobiose was greater for the microcrystalline cellulose than for the paper pulp. Even with high crystallinity, microcrystalline cellulose achieved the highest cellobiose yield probably due to its highest specific surface area accessible to enzymes and quantity of adsorbed protein.     

Lewis酸催化纤维素制乳酸机理研究

乳酸是制备可降解聚合物聚乳酸的主要单体。利用秸秆等原生生物质为原料经过化学催化转化制备乳酸对于碳减排具有重要意义。本工作利用同位素核磁和质谱详细探究了不同Lewis酸(Y³⁺,Sc³⁺,Al³⁺)催化纤维素制乳酸的反应选择性和机理。发现葡萄糖异构化为果糖的过程是决定纤维素制乳酸多步串联反应最终选择性的关键步骤,并明确了1, 3-二羟基丙酮生成乳酸经历了烯醇互变异构过程而非经典的1, 2-shift机理。     

Lewis酸催化纤维素制乳酸机理研究

Because fossil fuels are continuously depleted, valorization of biomass into valuable liquid products and chemicals is of great significance yet it remains challenging. Among many biomass-derived products, lactic acid is one of the most important renewable monomers for preparing the degradable polymer polylactic acid. The use of raw biomass to produce lactic acid through catalytic conversion is an attractive approach. In this work, the catalytic reaction performance and mechanism of different Lewis acids (Y³⁺, Sc³⁺, and Al³⁺) for the production of lactic acid from cellulose were investigated in detail by isotopic nuclear magnetic resonance (NMR) and mass spectrometry. The production of lactic acid from cellulose includes tandem and competing reactions. The order of catalytic activity for the one-pot conversion of cellulose into lactic acid is as follows: Y³⁺ > Al³⁺ > Sc³⁺. The main tandem reactions involve the hydrolysis of cellulose into glucose, the isomerization of glucose into fructose (the order of catalytic activity, the same below: Y³⁺ > Al³⁺, Y³⁺ > Sc³⁺), the cleavage of fructose via a retro-aldol reaction to glyceraldehyde (GLY) and 1, 3-dihydroxyacetone (DHA) (Sc³⁺ > Y³⁺ > Al³⁺), and the conversion of DHA or GLY to the final product lactic acid (Al³⁺ > Y³⁺ > Sc³⁺). It was found that the process of glucose isomerization to fructose was the key step to the final selectivity of the tandem reaction of cellulose conversion to lactic acid, and it was clarified that the production of lactic acid from DHA underwent a keto-enol (K-E) tautomerization process rather than a classical 1, 2-shift process. First, DHA was transformed into GLY via the isomerization process, then the adjacent hydroxyl group of GLY was removed in the form of water to produce an α, β-unsaturated species. After that, the α, β-unsaturated species underwent K-E tautomerization to generate unsaturated aldehyde-ketone intermediates. Meanwhile, a molecule of water was added to aldehyde-ketone intermediates to obtain a diol product, the hydrogen atom at the methine position was transferred and the lactic acid was finally obtained through the K-E tautomerization process. The in-depth understanding of the reaction mechanism presented in this work will help to design more selective catalysts for cellulose conversion into value-added oxygen-containing small molecule chemicals.      

甲酸为氢源的甘油催化选择氢解

以甲酸作为氢源, 采用铜基复合金属氧化物催化剂, 催化氢解甘油制备1,2-丙二醇, 其中液相甲酸的高选择性分解是实现甘油氢解的必要和关键步骤. 活性测试表明, 高分散的铜和ZrO₂载体间的协同作用对甲酸分解和甘油到1,2-丙二醇的转化至关重要, 20%Cu/ZrO₂催化剂的活性最佳. 由于避免使用相对昂贵的化石燃料氢, 因而该催化体系在生物质的高值利用方面具有潜在的应用前景.     

Self-reducing bifunctional Ni-W/SBA-15 catalyst for cellulose hydrogenolysis to low carbon polyols

A series of self-reducing bifunctional Ni-W/SBA-15 catalysts were synthesized using biomass-based carbon source as the reducing agent without conventional further reduction step. The self-reducing catalysts were performed on the hydrogenolysis of cellulose to low carbon polyols. The effects of calcination temperature and metallic loading contents for cellulose hydrogenolysis reaction were investigated detailedly.The optimal calcination temperature was found to be 673 K by TG analysis. The active metal nanoparticles with a better dispersion were observed using SEM and element mapping technology. The yield of low carbon polyols using the catalyst with the receipt of 10%Ni-15%W/SBA-15-673 K can reach as high as68.14%, of which the ethylene glycol(EG) accounts for 61.04%.