CMC稳定的Ni/Fe双金属催化体系的制备及对PCB77原位脱氯降解

以羧甲基纤维素钠(CMC)作为稳定剂,优化了制备条件,在反应温度25℃,m(CMC)/m(Fe)=5以及m(Ni)/m(Fe) =0.03的条件下成功制备了CMC-Ni/Fe纳米双金属颗粒.用制得的CMC-Ni/Fe纳米双金属颗粒于30℃下降解5 mg/L的PCB77溶液48 h,当双金属颗粒用量为3 g/L时,有高达94％的PCB77被降解,而没有加入CMC的Ni/Fe双金属体系只有71％的PCB77被降解.CMC-Ni/Fe纳米双金属颗粒经XRD检测,表现出明显的单质铁特征峰,且无铁氧化物特征峰,表明制备所得的纳米颗粒中的铁单质没有被氧化.经粒度分析仪的检测,CMC-Ni-Fe双金属纳米颗粒平均粒径在23.94 nm,明显小于没有加CMC的Ni/Fe双金属颗粒粒径(100 nm).     

Pd/Fe双金属对1,2,4-三氯苯的催化脱氯

采用Pd/Fe双金属体系对1,2,4-三氯苯（1,2,4-TCB）进行了快速催化还原脱氯的研究.结果表明,在钯的催化作用下,零价铁对1,2,4-TCB有较好的还原脱氯效率.当Pd/Fe双金属的钯化氯为0.06%时,催化剂用量为1g/40mL,反应1h后TCB的脱氯率可达99%.反应速率随钯化氯的提高而增加.反应在Pd/Fe表面进行,符合准一级反应,反应速率常数为0.0837min-1.TCB在催化脱氯的过程中先脱氯成为DCB,再依次脱氯为氯苯和苯.     

双金属异相催化剂Fe3O4@La-MOF-Schiff-Pd/Ni的制备及其催化Suzuki偶联反应

将Fe3O4纳米粒子负载到金属有机骨架La-MOF中,然后向其中引入Pd/Ni活性位点,制得含磁性纳米粒子的Pd/Ni双金属异相催化剂（Fe3O4@La-MOF-Schiff-Pd/Ni）,并通过SEM、TEM、EDS、ICP、PXRD和XPS对其进行了表征。结果表明,Fe3O4纳米粒子被成功嵌入到了La-MOF中,经过后合成修饰后,Pd和Ni活性位点被均匀分散在MOF框架中。该催化剂在Suzuki偶联反应中表现出较高的催化活性,以碘苯(1.0 mmol)和苯硼酸(1.2 mmol)为反应物时,最佳催化反应条件为：以无水乙醇为溶剂、无水碳酸钾为碱、反应温度80℃、反应时间为6 h、催化剂用量8 mg,在此条件下联苯产率达95%。该催化剂可以通过外加磁铁进行分离回收,经过5次循环使用后仍然保持较高的催化活性,产物产率为82%。Suzuki偶联反应机理探究结果表明,Pd和Ni可能具有协同催化效应。底物拓展实验表明,Fe3O4@La-MOF-Schiff-Pd/Ni双金属催化剂对含不同取代基的芳基溴化物和碘化物具有较好的普适性。     

醇水体系制备纳米Pd/Fe颗粒去除水中2,4-DCP

为了提高纳米铁的活性和分散性,在醇水体系下制备出纳米钯铁(Pd/Fe)双金属颗粒并表征,将制得的纳米Pd/Fe颗粒应用于水中2,4-二氯苯酚(2,4-DCP)的去除,考察了材料投加量、反应温度、初始pH值、2,4-二氯苯酚初始浓度等因素对2,4-DCP去除的影响,分析了2,4-DCP的去除机理并进行动力学拟合。结果表明,在醇水体系中制备纳米铁有利于纳米颗粒的稳定分散;钯的加入将脱氯途径转变为催化加氢,极大改善了2,4-DCP的去除效果;当2,4-DCP初始浓度为20 mg/L、反应温度30℃、纳米Pd/Fe颗粒投加量为2 g/L时,2,4-DCP可在5 h内去除99.9%;反应过程符合修正的一级反应动力学方程。     

生物还原法制备Pd/TiO2光催化剂

用芳樟叶煮液将PdCl2还原成Pd单质纳米颗粒,将其沉积于TiO2上制得Pd/TiO2催化剂,采用X射线衍射(XRD),扫描电镜(SEM)和能量色散谱仪(EDS)对催化剂进行表征,并以甲基橙为目标降解物评价Pd/TiO2催化剂的光催化降解活性.结果表明,Pd/TiO2催化剂中的Pd纳米颗粒的平均粒径小于10 nm,能够很好地分散在TiO2表面,且不改变TiO2锐钛矿的晶型结构.与未负载Pd的TiO2催化剂相比,Pd/TiO2光催化剂对甲基橙有更高的光催化降解活性,能够提高甲基橙的降解速率.在实验范围内.Pd与TiO2质量比为5%的催化剂活性最高,反应30 min甲基橙就能完全降解,而空白TiO2催化剂在反应1 h时降解率只达到95%.Pd与TiO2质量比为5%的Pd/TiO2光催化剂矿化率可达到96.2%,且重复使用仍能保持良好的催化活性.     

氧化石墨烯掺杂锌铝类水滑石负载钯金催化剂的制备及催化性能

采用离子交换-还原法制备了氧化石墨烯(GO)掺杂锌铝类水滑石负载钯金双金属纳米颗粒的催化剂(Pd Au/Zn-Al LDHs/GO),通过XRD、TEM表征了催化剂的结构,以GO掺杂锌铝类水滑石为载体负载钯金纳米颗粒粒径小(约2nm)且分散均匀。以苯甲醇空气氧化形成苯甲醛的反应为模型,评价催化剂的催化性能,探讨了载体及钯、金比例对催化反应的影响。催化结果表明,氧化石墨烯掺杂的锌铝类水滑石是考察载体中最好的钯、金催化剂的载体,随着钯金比的增加催化剂的催化活性先增加后降低,生成苯甲醛的选择性下降,当钯金比例为1∶1时,催化剂(Pd1Au1/Zn-Al LDHs/GO)的综合催化性能最好,催化活性随反应温度的升高而升高,但选择性随温度的升高而下降。在Pd1Au1/Zn-Al LDHs/GO催化下,80℃反应8h后苯甲醇的转化率可达96%,苯甲醛的选择性为93%,催化剂循环使用4次后仍保持较好的催化性能。     

低负载贵金属催化剂对二甲醚催化燃烧的催化活性

采用浸渍法以g-Al2O3为载体制备了多种低负载量的Pd和Pt催化剂,在微型固定床反应器装置上进行了二甲醚(DME)催化燃烧实验. 考察了不同贵金属负载量的Pd/g-Al2O3和Pt/g-Al2O3催化剂的活性,及浸渍顺序对Pd-Pt/g-Al2O3双金属负载催化剂活性的影响,并测试了贵金属负载摩尔比不同的双金属负载催化剂的活性. Pt负载量0.025%(w)的催化剂在190℃将DME完全燃烧;Pd和Pt共同负载的催化剂[Pd:Pt=2:1(mol), Pt 0.025%(w), Pd 0.027%(w), Pt先负载]性能更好,在175℃将DME完全燃烧;200 h实验后2种催化剂活性降低均小于5%.     

PAA-b-PS包埋纳米Fe/Ni材料的制备及其应用研究

合成了一种新材料聚丙烯酸-b-聚苯乙烯包埋纳米Fe/Ni颗粒(PAA-b-PS-Fe/Ni),并对1,1,1-三氯乙烷(1,1,1-TCA)的选择性脱氯效果进行了评价。由于PAA-b-PS可以防止零价铁团聚,PAA-b-PS包埋纳米Fe/Ni双金属颗粒的平均尺寸约为50 nm。在1. 0 g/L Fe/Ni(Ni/Fe质量比为2%)和0. 5 g/L PAA-b-PS的包埋质量浓度下,脱氯反应在240 min后达到平衡,并对200 mg/L的1,1,1-TCA的去除效率最佳(87. 5%)。PAA-b-PS-Fe/Ni对1,1,1-TCA的去除效率与无机阴离子(NO-3、HCO-3和SO_2-4)无关,去除效率均约为88%。然而,腐植酸对1,1,1-TCA的降解有很大影响。总之,PAA-b-PS包埋纳米Fe/Ni颗粒具有选择性,并且对于降解地下水中1,1,1-TCA非常有效。     

水热法制备铁炭复合材料及其对地下水中三氯乙烯的降解性能

以蔗糖和无水三氯化铁为原料，以氨水调节溶液pH，采用水热-炭化法在不同pH下合成了系列铁炭复合材料(Fe/C pH2、Fe/C pH4、Fe/C pH6、Fe/C pH8、Fe/C pH10)。进一步将Fe/C pH10球磨为粒径分布在100~1000nm的铁碳复合材料（Fe/C pH10-Q）。考察了各个产物对三氯乙烯的吸附和降解性能。采用SEM、XRD、TG、N2吸附-脱附对不同pH下制备的产物形态和组成进行了表征。采用气相色谱(GC)和离子色谱(IC)对污染物三氯乙烯和降解产物乙烷、乙烯、氯离子进行了定量检测。结果表明，复合材料中纳米零价铁（nZVI）和生物炭共同存在，nZVI被随机分散在碳球或碳颗粒上，不发生团聚现象。随着反应液pH的增加，产物中nZVI的含量和粒径从Fe/C pH2的6.52%、20 nm增加到Fe/C pH10的36.35%、60 nm，比表面积由Fe/C pH2的369 m2/g 减小到Fe/C pH10的302 m2/g。不同pH下制得Fe/C复合材料对TCE降解速率大小顺序为：Fe/C pH10＞Fe/C pH8＞Fe/C pH6＞Fe/C pH4＞Fe/C pH2。48h的反应时间下， Fe/C pH10对TCE的去除率可接近100%。球磨不会改变Fe/C复合材料中nZVI粒径、含量和材料的反应活性。通过石英砂柱评价了Fe/C pH10-Q的传输性能，其具有良好的地下传输性能。与市售nZVI和Fe/C pH10相比，其流动性显著提高。     

双金属Co/Pd纳米催化剂催化乙炔双羰化反应的性能研究

采用一步还原法制备了一系列双金属纳米Pd基合金催化剂,以获得优秀的乙炔双羰化反应催化剂。利用透射电子显微镜(TEM)、X-射线光电子能谱(XPS)、X-射线衍射(XRD)、原位红外光谱(In-situ IR)等手段对催化剂的性质进行了研究。考察了掺杂金属、溶剂、助剂种类及用量、一氧化碳压力、温度对反应产率的影响。结果表明:以乙腈为溶剂,乙炔、一氧化碳和甲醇为原料合成丁烯二酸二甲酯,Co/Pd双金属纳米催化剂的活性最高,在低温低压条件下丁烯二酸二甲酯的总产率可达97.99%。Co元素的引入,有助于降低Pd对一氧化碳吸附强度,使更多的吸附于催化剂表面的CO分子能参与反应,提高了Pd基纳米双金属催化剂催化乙炔双羰化反应的活性。     

Treatment of chlorinated organic contaminants with nanoscale bimetallic particles

Nanoscale bimetallic particles (Pd/Fe, Pd/Zn, Pt/Fe, Ni/Fe) have been synthesized in the laboratory for treatment of chlorinated organic pollutants. Specific surface areas of the nanoscale particles are tens of times larger than those of commercially available microscale metal particles. Rapid and complete dechlorination of several chlorinated organic solvents and chlorinated aromatic compounds was achieved by using the nanoscale bimetallic particles. Evidence observed suggests that within the bimetallic complex, one metal (Fe, Zn) serves primarily as electron donor while the other as catalyst (Pd, Pt). Surface-area-normalized reactivity constants are about 100 times higher than those of microscale iron particles. Production of chlorinated byproducts, frequently reported in studies with iron particles, is notably reduced due to the presence of catalyst. The nano-particle technology offers great opportunities for both fundamental research and technological applications in environmental engineering and science.     

Hydrodechlorination of trichloroethene using stabilized Fe-Pd nanoparticles: Reaction mechanism and effects of stabilizers, catalysts and reaction conditions

This study investigated the effects of carboxymethyl cellulose (CMC) as a stabilizer on the reactivity of CMC-stabilized Fe-Pd bimetallic nanoparticles toward trichloroethene (TCE). Overall, the particle stabilization prevented particle agglomeration and resulted in greater particle reactivity. The pseudo-first order TCE degradation rate increased from 0.86 h⁻¹ to 6.8 h⁻¹ as the CMC-to-Fe molar ratio increased from 0 to 0.0124. However, a higher CMC-to-Fe ratio inhibited the TCE degradation. Within the same homologous series, CMC of greater molecular weight resulted in more reactive nanoparticles for TCE hydrodechlorination. Hydrogen (either residual hydrogen from zero-valent iron (ZVI) nanoparticle synthesis or hydrogen evolved from ZVI corrosion) can serve as effective electron donors for TCE dechlorination in the presence of Pd (either coated on ZVI or as separate nanoparticles). Decreasing reaction pH from 9.0 to 6.0 increased the TCE reduction rate by 11.5 times, but enhanced the Fe corrosion rate by 31.4 times based on the pseudo-first order rate constant. Decreasing pH also shifted the rate controlling step of TCE reduction from Fe corrosion to hydrodechlorination. Ionic strength (<0.51 M) did not significantly affect the TCE reduction.     

PdAg、PdAu合金纳米晶的制备及其催化性能研究

采用硼氢化钠一步还原法,首先得到PdAg和PdAu双金属合金纳米颗粒.利用XRD、TEM以及紫外可见光光谱技术对其进行了表征分析.结果表明,PdAg和PdAu两种合金都具有纳米颗粒分散均匀且颗粒尺寸小等优点.随后采用胶体沉积法将两种合金均匀地负载到Al2O3上,成功获得PdAg/Al2O3和PdAu/Al2O3两种金属纳米催化剂.在邻氯硝基苯加氢反应中,与Pd/Al2O3纳米催化剂相比,PdAg/Al2O3催化剂显示出95.5％的选择性,而PdAu/AI2O3催化剂的选择性高达98.7％,这可能归因于Pd与Ag或Au金属间的协同效应.     

Catalytic Oxidation of Polyethylene Glycol Dodecyl Ether to Corresponding Carboxylic Acid by Gold, Palladium (Mono and Bimetallic) Nanoparticles Supported on Carbon

Mono and bimetallic catalysts based on Au and Pd nanoparticles were synthesized by sol immobilization method. The catalytic oxidation of polyethylene glycol dodecyl ether was performed using as-synthesized supported catalyst. The use of water as solvent and dioxygen as oxidant makes the reaction interesting from both an economic and environmental point of view. For 100 min, the conversion of polyethylene glycol dodecyl ether using Au–Pd/C bimetallic catalyst was 38%, showing an increase of 9% for Au/C and 15% for Pd/C respectively indicating that a synergetic effect exists between Au and Pd. For the Au–Pd/C catalyst, adding Au after the prior addition and reduction of Pd metal can form the most active catalyst.     

Iron-Based Nanoparticles for Toxic Organic Degradation: Silica Platform and Green Synthesis

Iron and iron oxide nanoparticles (NPs) are finding wide applications for the remediation of various toxic chloro-organic compounds (such as trichloroethylene, TCE), via reductive and oxidative processes. In this study, Fe NPs (30-50 nm) are synthesized by reduction from ferric ions immobilized (by ion exchange) on a platform (two types of sulfonated silica particles), in order to prevent the NP agglomeration. Next, the Fe NPs are oxidized and their effectiveness for the oxidative dechlorination of TCE via the heterogeneous decomposition of hydrogen peroxide to OH? on the surface of the iron oxide NPs was demonstrated. For the reductive approach, the use of ascorbic acid as a "green" reducing agent in conjunction with a secondary metal (Pd) inhibits NP oxidation and agglomeration through surface adsorbed species. The Fe/Pd NPs have been successfully applied for the dechlorination of TCE (k(SA), surface-area normalized reaction rate, = 8.1 ×10(-4) L/m(2)h).     

Pd/Fe双金属对水中m-二氯苯的催化脱氯

引　言氯代芳烃及其衍生物化学性质稳定 ,易在生物体内累积 ,大多被列为美国EPA环境优先控制污染物 ,一旦进入环境将对人类及其生态环境造成长期威胁 .因此 ,氯代芳烃的治理技术日益引起全球的关注[1] .自 2 0世纪 80年代末提出金属铁屑用于地下水的原位修复以来[2 ,3] ,用Fe0 还原脱氯已成为一个非常活跃的研究领域 ,特别是应用于地下水修复方面的研究 .Fernando等[4～ 7] 将双金属催化剂用于有机氯的催化还原脱氯 ,Fe0 表面的Pd或Ni等金属加速了还原脱氯反应 ,脱氯速率比Fe0 体系快得多 .本研究利用Pd/Fe双金属对m DCB进行了催化还…     

Trimetallic nanoparticles having a Au-core structure

The Au/Pt/Rh trimetallic nanoparticles were successfully synthesized by a combination of a co-reduction and a self-organization method using poly(N-vinyl-2-pyrrolidone) (PVP) as a protecting reagent. The triple core/shell structure was suggested by HR-TEM, EF-TEM and FT-IR-CO for the trimetallic nanoparticles. The present trimetallic nanoparticles had much higher catalytic activity for hydrogenation than the corresponding monometallic and bimetallic nanoparticles. This high catalytic activity can be due to the sequential electronic effect between different atoms of a particle, which is supported by XPS data.     

Synthesis of bimetallic PdAu nanoparticles for formic acid oxidation

In this work, a simple co-deposition strategy for the synthesis of carbon-supported Pd–Au alloy was reported. Our approach involves the co-reduction of Au and Pd ions using ethylene glycol and sodium citrate as the reducing and stabilizing reagents. Both alloy and non-alloy bimetallic Pd–Au nanoparticles are produced using a right rate-limiting strategy. For example, when ethylene glycol and sodium citrate are the limiting reagent with Au and Pd ions in excess, the synthesis environment favors preferential nucleation and growth of Au nanoparticles followed by deposition of Pd either as the shell of Au core or as separate Pd clusters. On the other hand, if the supply of metal ions (not the reducing reagents) limits the reaction, it creates a synthesis condition for Pd–Au alloy particles. The as-prepared Pd–Au alloys exhibit higher Pd-specific activities towards formic acid oxidation compared with the non-alloy counterpart or individual Pd catalyst and an easier removal of adsorbed oxygen species (e.g., O_ads or OH_ads) was observed from the surface of Pd–Au alloy with a higher content of Au.     

Effects of Supports and Promoter Ag on Pd Catalysts for Selective Hydrogenation of Acetylene

SiO2, a-Al2O3, g-Al2O3, ZrO2 and CeO2 were used as supports and Ag as promoter to study their effects on Pd catalysts for selective hydrogenation of acetylene. The catalysts were prepared by impregnated synthesis and characterized by XRD, BET and TEM. The catalytic reaction was carried out in a fixed-bed reactor. Overall, the low specific surface area supports were better to increase the ethylene selectivity at high conversion rate of acetylene. Among the four Pd catalysts on low specific surface area supports, the catalyst on low specific surface area SiO2 (LSA-SiO2) retained a high ethylene selectivity even at complete conversion, while the other catalysts showed significant decrease in the selectivity at complete conversion. The performance of Pd/LSA-SiO2 was important to decrease the loss of ethylene in selective hydrogenation of trace acetylene in ethylene. Addition of Ag to Pd/LSA-SiO2 significantly decreased the formation of ethane, C4 alkenes and green oil, and improved the ethylene selectivity to 90% when Pd:Ag=1:1 and 1:3(w). When the ratio of Pd to Ag was above 1, the activity of Pd-Ag bimetallic catalyst was similar to that of Pd monometallic catalyst, and the selectivity of ethylene increased with increasing of amount of Ag. When the ratio of Pd to Ag was below 1, the activity of bimetallic catalyst decreased with increasing of amount of Ag, while the selectivity of ethylene was kept unchanged. The optimum temperature was 200~230℃ for 0.02%(w)Pd-0.02%(w)Ag/LSA-SiO2 to give a high ethylene selectivity and low formation of green oil.