复合材料Au/Cu2O的合成及其光催化CO2还原为CO活性研究

采用多元醇法制备不同质量百分比Au/Cu₂O催化剂，通过SEM、TEM、XPS等手段对复合材料的理化性质进行表征。在紫外-可见光照射下进行CO₂光还原实验研究。光还原实验表明，与纯Cu₂O相比，3%Au/Cu₂O具有优良的光催化性能。反应4 h后CO产量可达3.5μmol/g,比纯Cu₂O的产量高1.4倍。通过对其光学和电化学性能进行测试表明3%Au/Cu₂O的各项性能均优于纯Cu₂O。这归因于Au/Cu₂O催化剂光吸收性能的提高及Au纳米粒子作为助催化剂捕获Cu₂O堆积的多余电子从而促进催化剂光生载流子的分离与迁移，使得催化性能大大提高。     

气流磨制备微纳米氧化亚铜及其防污性能研究

采用气流磨处理工业级 Cu₂O,可有效减小颗粒粒径和分布范围,得到平均粒径约为 0.98 μm的微纳米 Cu₂O;通过抑菌、抑藻、铜离子渗出速率、浅海浸泡等试验探讨了微纳米Cu₂O防污性能。结果表明：相对于工业级 Cu₂O,微纳米 Cu₂O的 24 h抑菌、抑藻率可分别提升约 28.82%和 21.82%,使防污涂料具有更优异的实海综合应用性能和防污性能;相对于纳米级 Cu₂O,基于微纳米 Cu₂O的防污涂层具有更稳定、可控的铜离子渗出性能,避免了因纳米 Cu₂O引起的前期铜离子“暴释”而导致的资源浪费,以及后期铜离子渗出率不足而导致的防污效果欠佳等缺陷。     

可见光催化剂改性粘胶基活性炭纤维脱硫脱硝试验

采用水合肼还原法制备了TiO₂/Cu₂O复合光催化剂，并将其负载在活性炭纤维(ACF)上。利用SEM、XPS、BET和XRD分析了催化剂的性能变化和反应行为。考察了催化剂对NO和SO₂的去除效率。结果表明，TiO₂/Cu₂O改性后ACF的孔径减小。表面官能团包括石墨碳和羰基的增加，提高了活性炭纤维对NO和SO₂的吸附能力。在可见光下，当温度为40℃时，TiO₂/Cu₂O脱硫脱硝效率最高，分别为90%和60%。     

Cu2O/TiO2催化甲醛乙炔化反应的载体效应

以不同温度焙烧的TiO₂为载体,CuCl₂·2H₂O为铜源,NaOH为沉淀剂,L-抗坏血酸钠为还原剂,采用液相还原-沉积沉淀法制备了Cu₂O/TiO₂,借助X射线粉末衍射（XRD）、H₂程序升温还原（H₂-TPR）、N₂-物理吸附、透射电镜（TEM）、X射线光电子能谱（XPS）等手段,研究了TiO₂载体焙烧温度对Cu₂O/TiO₂甲醛乙炔化反应性能的影响。结果表明,低温焙烧得到的TiO₂载体以锐钛矿相存在,与Cu₂O物种间具有弱的相互作用,使得Cu₂O被过度还原为金属Cu,催化活性较低。随着载体焙烧温度的升高,TiO₂中出现金红石相,Cu₂O与载体间相互作用增强,Cu₂O高效转变为乙炔亚铜活性物种,使催化剂表现出最佳的催化性能。     

纳米氧化亚铜的形貌控制合成及光催化降解有机染料的研究进展

回顾了近年来不同形貌Cu₂O纳米晶体、Cu₂O纳米笼和纳米骨架的合成及最新研究进展,着重介绍了一维Cu₂O纳米材料的合成过程,比较了不同形貌Cu₂O的制备方法并指出了合成的关键步骤。比较了不同形貌Cu₂O晶体的光催化性能,总结指出具有更多高活性{110}晶面或高指数晶面的Cu₂O晶体有显著的光催化性能。最后总结了不同形貌Cu₂O的控制合成方法,指出Cu₂O的可控合成机理研究、非传统多晶面的Cu₂O及具有完整晶面Cu₂O纳米笼的合成是未来的研究重点;提出Cu₂O在光催化领域的主要问题是稳定性较差且光催化效率不高。     

绿茶水热还原制备微纳米金属铜

以绿茶茶水兼为溶剂和还原剂,采用水热法直接还原制备出不同形貌的微纳米金属Cu粉,同时研究了pH、茶水浓度（茶粉与水的质量比）、水热温度以及TiOSO₄对微纳米Cu的相纯度和颗粒形貌的影响。研究结果表明:在pH=3～12、m(茶)∶m(H₂O)=1∶100,反应温度为200℃的条件下,均可得到聚集态的球状金属Cu;降低茶水的浓度或反应温度,产物中存在Cu和Cu₂O两相,且随着茶水浓度或反应温度的降低,产物中Cu₂O的相对含量均逐渐升高;另外,在一次水热合成获得的单相Cu₂O中加入0.1gTiOSO₄并经过200℃、24h二次水热处理后,制备出长度为10～40μm、直径为0.4～0.9μm的一维棒状金属Cu。     

Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原

电催化二氧化碳还原是降低大气中二氧化碳浓度和缓解温室效应的有效方法。然而，将CO₂电还原为具有高附加值和高能量密度的碳氢化合物或燃料(C₂₊产物)仍然具有十足的挑战性。为了降低大气中二氧化碳浓度和将其转换为有价值的工业品，本文通过优化Ag/Cu耦合催化剂中Cu的晶面，有效地促进了其还原CO₂至C₂H₄和C₂H₅OH等C₂₊产物。利用暴露Cu₂O(100)晶面的Ag/Cu₂O-(100)，暴露Cu₂O(111)晶面的Ag/Cu₂O-(111)以及具有Cu₂O(100)和(111)晶面的Ag/Cu₂O-(100/111)还原制备得到了三种具有不同Cu晶面的Ag/Cu耦合催化剂。控制Cu/Ag比均为30∶1，采用H型电解槽，在CO₂饱和的0.1mol/L KHCO     

基于CuAl-LDH载体制备高分散Cu/ZnO/Al2O3催化剂及其催化性能

通过沉积沉淀法制备了以层状CuAl-LDH为载体负载不同Cu/Zn比例的前体,经热处理得到CuZnAl-LDO复合催化剂,应用于合成气制甲醇反应。采用电感耦合等离子体发射光谱（ICP）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、N₂O化学吸附、N₂吸脱附、透射电镜（TEM）和X射线光电子能谱技术（XPS）等手段对前体及催化剂进行表征,考察了水滑石的限域效应和金属-载体相互作用对催化剂活性及稳定性的影响。结果发现：由于水滑石特殊的层状结构,具有较大比表面积和丰富孔道结构,促进了Cu物种的分散,有利于催化剂表面对CO和H₂的吸附,增加了Cu、Zn之间的相互作用,提高了催化剂的催化活性。在水滑石前体拓扑转变过程中,层板羟基和水脱除后形成的粗糙表面对所负载的Cu活性物种起到限域作用,抑制了Cu的迁移和团聚。其中,Cu_0.6Zn_0.3Al_0.1-LDO催化剂催化合成甲醇的时空收率达到883mg/(g?h),且反应120h后仅下降2.8%,较共沉淀制备催化剂失活速率降低了81%,表现出较好的催化活性及稳定性。     

Cu2O纳米微晶玻璃的显微结构及性能研究

新型Cu₂O纳米微晶玻璃具有高Cu载量、低成本和易大规模制备等特点，有望成为载银抗菌玻璃较有潜力的替代者。通过采用XRD、Raman光谱、XPS、FESEM和TEM等表征方法重点研究了不同ZnO/K₂O比对SiO₂-Al₂O₃-K₂O-ZnO-P₂O₅-B₂O₃-CuO微晶玻璃显微结构的影响，并分析讨论了其结构-性能关系。结果表明，微晶玻璃中Zn与P元素会富集在Cu元素所在区域的附近，适量的ZnO能使微晶玻璃中析出的Cu₂O晶粒尺寸稳定在纳米级别，并能调节微晶玻璃中Cu元素的浸出速率。Cu₂O纳米微晶玻璃对大肠杆菌和金黄色葡萄球菌均具有显著的抗菌效果，并能实现对维多利亚蓝B溶液的可见光催化降解，是一种极具发展潜力的新型功能微晶玻璃材料。     

MOF作模板制备多孔Au/CuxO催化剂及其CO氧化性能

采用MOF材料作模板,通过在Cu-BTC材料表面预先负载贵金属Au再热解的方法,成功制备了具有正八面体结构的新型多孔Au/Cu_xO负载型催化剂。通过降低热解环境中的O₂浓度,调节氧化时间,实现了Au/Cu-BTC氧化产物组分的调节,分别制得了Au/Cu₂O、Au/Cu₂O-CuO、Au/CuO复合催化材料。将其用于CO催化氧化,发现所有Au/Cu_xO催化剂都表现出比Cu-BTC和Au/Cu-BTC更优异的催化性能,其中由于拥有较高的比表面积、Cu₂O含量以及更好的Au的分散性,Au/Cu₂O的CO氧化活性最佳,180℃即能实现CO的完全转化。     

Insight into the promotional mechanism of Cu modification towards wide-temperature NH3-SCR performance of NbCe catalyst

A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu_0.010/Nb₁Ce₃ presented over 90% NO conversion in a wide temperature range of 200-400 ℃ and exhibited an excellent H₂O or/and SO₂ resistance at 275 ℃. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO₄ and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu²⁺, the isolated Cu²⁺ acted as catalytic active sites to promote the reaction: Cu²⁺-NO₃^-+NO(g) → Cu²⁺-NO₂^-+NO₂(g). Then the generated NO₂ would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH₃, and ensuring the improvement of catalytic activity at high temperature. Since the NH₃-SCR reaction followed by E-R reaction pathway efficaciously over Cu_0.010/Nb₁Ce₃ catalyst, the excellent H₂O and SO₂ resistance was as expected.     

Magnetic graphene oxide-anchored Ni/Cu nanoparticles with a Cu-rich surface for transfer hydrogenation of nitroaromatics

The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell (Ni/Cu NPs) were successfully synthesized by a liquid-phase thermal decomposition method. The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors, copper formate (Cuf) and nickel acetate tetrahydrate (Ni(OAc)₂·4H₂O). Ni/Cu NPs were further anchored on graphene oxide (GO) to prepare a magnetic composite catalyst, called Ni/Cu-GO. The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process, thereby ensuring the catalytic and cycling performance of the catalyst. The catalytic transfer hydrogenation (CTH) reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source. Cu dominated the main catalytic role in the reaction, while Ni played a synergistic role of catalysis and providing magnetic properties for separation. The Ni₇/Cu₃-GO catalyst exhibited the best catalytic performance with the conversion and yield of 99% and 96%, respectively, when 2-methyl-5-nitrophenol was used as the substrate. The Ni₇/Cu₃-GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90% after six cycles. In addition, the Ni₇/Cu₃-GO catalyst could be quickly recycled by magnetic separation. Moreover, the Ni₇/Cu₃-GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.     

Facile synthesis of hierarchical flower-like Ag/Cu2O and Au/Cu2O nanostructures and enhanced catalytic performance in electrochemical reduction of CO2

Novel, hierarchical, flower-like Ag/Cu₂O and Au/Cu₂O nanostructures were successfully fabricated and applied as efficient electrocatalysts for the electrochemical reduction of CO₂. Cu₂O nanospheres with a uniform size of ~180 nm were initially synthesized. Thereafter, Cu₂O was used as a sacrificial template to prepare a series of Ag/Cu₂O composites through galvanic replacement. By varying the Ag/Cu atomic ratio, Ag_0.125/Cu₂O, having a hierarchical, flower-like nanostructure with intersecting Ag nanoflakes encompassing an inner Cu₂O sphere, was prepared. The as-prepared Ag_x/Cu₂O samples presented higher Faradaic efficiencies (FE) for CO and relatively suppressed H₂ evolution than the parent Cu₂O nanospheres due to the combination of Ag with Cu₂O in the former. Notably, the highest CO evolution rate was achieved with Ag_0.125/Cu₂O due to the larger electroactive surface area furnished by the hierarchical structure. The same hierarchical flower-like structure was also obtained for the Au_0.6/Cu₂O composite, where the FE_CO (10%) was even higher than that of Ag_0.125/Cu₂O. Importantly, the results reveal that Ag_0.125/Cu₂O and Au_0.6/Cu₂O both exhibit remarkably improved stability relative to Cu₂O. This study presents a facile method of developing hierarchical metal-oxide composites as efficient and stable electrocatalysts for the electrochemical reduction of CO₂.     

不同烟气组分对粉状活性焦吸附汞的影响机理

在模拟燃煤热烟气为热源和介质条件下，以准东褐煤为原料，通过一维沉降炉进行炭化活化（一步法）制备粉状活性焦，考察了活性焦对Hg⁰的吸附能力，探索了SO₂、H₂O、O₂、CO₂、H₂O+O₂、SO₂+O₂及H₂O+SO₂+O₂气氛对活性焦吸附Hg⁰的影响机理。结果表明：一步法获得的活性焦对Hg⁰具有较高的吸附性能。N₂气氛作对比，H₂O、H₂O+O₂、CO₂和SO₂气氛下抑制活性焦对Hg⁰的吸附；O₂、SO₂+O₂和H₂O+SO₂+O₂促进活性焦对Hg⁰的吸附。通过Hg 4f的XPS分析证明了不同气氛组成对活性焦吸附Hg⁰的抑制和促进机理。H₂O覆盖在活性焦活性位上和堵塞孔隙而抑制活性焦对Hg⁰的吸附；SO₂与Hg⁰在活性焦上发生竞争吸附而抑制对Hg⁰的吸附；CO₂ 吸附在活性焦微孔上而抑制对Hg⁰的吸附；O₂气氛下主要形成了HgO, SO₂+O₂气氛下Hg⁰被氧化成HgSO₃，进一步氧化成HgSO₄； H₂O+SO₂+O₂气氛下，Hg⁰被氧化成HgO和HgSO₄。     

氧化亚铜基复合光催化剂的研究进展

氧化亚铜在光催化、太阳能电池、传感器等领域有着广阔的应用前景。结合氧化亚铜光催化剂的研究方向,综述了改善其光催化性能的常用方法,包括形貌尺寸改进、掺杂、金属负载和半导体复合等。介绍了几种具有代表性的氧化亚铜基复合光催化剂,包括金属-氧化亚铜复合光催化剂、氧化亚铜-半导体复合光催化剂、氧化亚铜-碳材料复合光催化剂和三元复合光催化剂,阐述了它们各自的反应机理。最后对氧化亚铜基复合光催化剂今后的发展进行了展望。     

铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢性能研究

采用浸渍-还原法制备了铁、钴、镍、铜和锌催化剂,考察了其催化氨硼烷水解产氢性能,并优化了钴催化剂的制备条件和反应条件。结果发现,铁催化剂中铁以Fe₂B合金相存在,钴催化剂中钴以金属钴存在,镍催化剂中镍以金属镍和Ni（OH）₂·2H₂O存在,铜催化剂中铜以金属铜和氧化亚铜存在,锌催化剂中锌以Zn₄SO₄（OH）₆·4H₂O存在。铁、钴、镍、铜和锌催化剂催化氨硼烷水解产氢活性由大到小顺序为钴催化剂、镍催化剂、铜催化剂、铁催化剂、锌催化剂。显然,具有金属钴相的钴催化剂、金属镍相的镍催化剂和金属铜相的铜催化剂催化氨硼烷产氢活性高于具有Fe₂B合金相的铁催化剂。锌催化剂在制备条件下不能被还原为金属相,它几乎没有催化氨硼烷产氢活性。氯化钴与还原剂硼氢化钠的物质的量比为1∶1.3、还原温度为303 K时制备的钴催化剂催化BH₃NH₃水解产氢性能最佳。反应动力学计算表明钴催化剂催化BH₃NH₃水解产氢反应对氨硼烷浓度的反应级数为零级,对钴催化剂浓度的反应级数为一级,活化能为58 kJ/mol。     

Cu2O催化甲醛乙炔化反应助剂效应

在液相还原法制备的纯Cu2O样品中,采用浸渍法分别引入Mg、Al、Fe助剂制备Cu2O-MgO、Cu2O-Al2O3、Cu2O-Fe2O3催化剂。采用XRD、FT-IR、TEM和H2-TPR等对催化剂进行表征,研究不同助剂的加入对甲醛乙炔化反应的影响。结果表明,不同助剂对催化剂的结晶度和可还原性能有较大影响,进而使甲醛乙炔化表现出不同的催化活性。相比MgO与Al2O3,Fe2O3的引入,使Cu2O结晶度明显下降,主要是由于Fe2O3与Cu2O之间产生强的相互作用,有利于乙炔亚铜活性物种的形成,从而表现出最优的催化性能。