不同晶面Cu_2O光催化还原Cr(VI)的性能（英文）

Cr(VI)具有高毒性和强诱变致癌性,且能稳定存在于自然界中,对人类和自然环境危害极大.而容易沉淀和吸附在固体上的Cr(III)毒性较小,约为Cr(VI)的千分之一.因此,将Cr(VI)还原为Cr(III)是处理含铬废水的有效途径.光催化还原是一种环境友好的新型技术,基于可见光的催化还原处理含Cr(VI)废水能够在常温常压下进行,具有经济、高效、清洁和无二次污染等特点而受到广泛关注.采用适宜的晶面生长控制剂,调变不同晶面的相对生长速率,可制得暴露不同晶面、具有多种形貌的Cu2O.将这些具有不同晶面的Cu2O用于光催化氧化降解有机污染物的研究表明,Cu2O的光催化氧化性能与其所暴露的晶面密切相关,其表面残留的用作晶面生长控制剂的表面活性剂对其催化性能有重要影响.相对而言,将Cu2O用于光催化还原Cr(VI)的研究较少,关于晶面导向剂油酸对其光催化还原Cr(VI)性能的影响尚未见报道.本文采用液相法,首先合成了仅暴露Cu2O{100}晶面的立方体(Cub),进而通过控制晶面导向剂油酸的用量,制得仅外露Cu2O{111}晶面的八面体(OctO)和仅暴露Cu2O{110}晶面的十二面体(Rhd O),继而再将OctO和Rhd O在C3H6-O2等混合气中于215o C处理30 min,通过此温和氧化除去表面油酸,获得了具有洁净表面的八面体(Oct)和十二面体(Rhd)的Cu2O.采用X射线衍射(XRD)、扫描电镜(SEM)和傅里叶变换红外光谱(FT-IR)等技术对其物性特征进行了表征.在LED可见光辐照下,对比评价了具有不同晶面的Cu2O光催化还原Cr(VI)的性能,研究了暴露晶面及晶面导向剂油酸等对Cu2O光催化还原Cr(VI)的影响.XRD研究表明,采用液相法及温和氧化处理可制得纯相的Cu2O,其XRD图中无Cu及Cu O等杂峰出现.SEM观测结果表明,所得Cu2O样品形貌均一性较好,采用丙烯选择氧化去除表面油酸后,Cu2O的形貌无明显改变,仅其外表面略有粗化.FT-IR分析进一步说明,去除表面油酸后,其物相仍为Cu2O,没有出现CuO的红外特征吸收.动力学研究结果显示,Cu2O光催化还原Cr(VI)具有准一级反应动力学特征,晶面导向剂油酸的存在能够在一定程度上减缓光腐蚀和酸腐蚀,有助于较长时间内保持Cu2O光催化还原活性,而对Cu2O光催化速率没有影响.以单位比表面积速率常数为比活性指标,不同晶面Cu2O光催化还原Cr(VI)的活性次序为{111}{110}{100}.Cu2O不同晶面的原子配位情况差异明显,且{100}晶面的表面能较低,由此可较好解释具有不同晶面Cu2O光催化还原Cr(VI)活性的不同.八面体Cu2O的{111}面上同时存在配位饱和与配位不饱和Cu,而菱形十二面体Cu2O的{110}面上只有配位饱和Cu,立方体Cu2O的{100}面上只有配位不饱和O.相对于Cu2O的{100}晶面,具有更高表面自由能的{111}和{110}晶面易于产生光生电子-空穴对,从而表现出较{100}晶面更高的光催化活性.而Cu2O{111}晶面表现出更高光催化活性的原因可能是:Cu2O{111}晶面上存在的不饱和Cu可作为活性位点,在某种程度上有利于光生电子-空穴对分离,减少光生电子-空穴对复合,从而提高光催化还原速率.     

{111}晶面暴露对介孔金红石TiO_2单晶光催化产氢的促进作用（英文）

光催化反应发生在半导体材料的表面,材料表面的原子/电子结构直接影响光催化剂的活性或选择性.因此,发展具有特定晶面的半导体光催化剂受到各国学者的普遍关注,被认为是调控光催化材料性能的有效途径之一.自2008年yang等首次合成高表面能{001}晶面占优的锐钛矿Ti O2单晶以来,控制合成暴露不同晶面Ti O2晶体的研究得到了迅猛的发展,已发展了多种方法合成了具有不同晶面的Ti O2晶体.研究表明,选择性地暴露特定的活性晶面能够显著地提高光催化剂的活性或者改变光催化反应的选择性.但是,含有完整晶面构型的Ti O2单晶样品的颗粒尺寸一般都较大,通常为几微米,因而显著增加了光生载流子传输与分离的难度,并且导致材料较小的比表面积,限制了对光催化活性的进一步提高.能否在合成含特定晶面单晶的同时增加多孔结构成为有效解决这一问题的关键.最近,Crossland等采用晶种模板法成功合成了介孔的锐钛矿Ti O2单晶,并且通过光电器件研究证实了采用该思路可进一步提高材料的光电性能.金红石Ti O2在光催化全分解水方面具有独特的优势,然而关于多孔单晶金红石Ti O2的研究相对较少,尤其是合成热力学不稳定的高表面能{111}晶面完全暴露的多孔金红石单晶面临较大的技术挑战因而一直未见文献报道.本文利用晶种模板法,以Ti Cl4溶液为含Ti前驱体、Na F为形貌控制剂、采用水热处理制备出不同比例{111}晶面的介孔金红石单晶.我们前期工作表明,Na F可作为形貌控制剂合成低表面能{110)晶面占优的介孔金红石单晶.本文发现,通过改变Na F的添加量,可有效调变{111}/{110}晶面比例,最终合成完全暴露{111}高表面能的介孔金红石Ti O2单晶.扫描电镜结果显示,当添加20 mg NaF时,合成{110}占优的具有高长径比的介孔晶体;当Na F用量增加到40 mg时{110}晶面进一步缩短;至80 mg时则制备出{111})高能面完全暴露的金红石Ti O2晶体.值得注意的是,对比研究表明,不采用模板合成了与多孔晶体完全相对应的不同{111}/(110}晶面比例的实心金红石晶体.透射电镜及选区电子衍射以及结合X射线衍射进一步证实,多孔的金红石Ti O2晶体与实心金红石单晶均都为单晶结构,孔结构贯穿于样品内部且具有较高的晶面结晶性.氮气吸附实验发现,虽然三个不同晶面比例介孔金红石单晶样品间的形貌具有显著的差异,但比表面积非常相近(分别为24,25,28 m2/g),孔径也都为50 nm左右,该值与所用SiO 2模板球的直径以及TEM观察结果相一致.光催化产氢性能结果表明,选择性的暴露活性晶面显著提高了光催化活性,仅含高能面{111}的介孔金红石单晶样品具有最高的产氢速率(约800μmol h–1 g–1),比常规{110}晶面占优的介孔单晶样品速率提高了约一倍.尤其比实心单晶样品的产氢速率提高了至少一个数量级,这应归结于介孔结构特性所导致的表面反应活性位增加、电子传输距离缩短以及光吸收增强协同作用的结果.     

{111}晶面暴露对介孔金红石TiO2单晶光催化产氢的促进作用

光催化反应发生在半导体材料的表面,材料表面的原子/电子结构直接影响光催化剂的活性或选择性。因此,发展具有特定晶面的半导体光催化剂受到各国学者的普遍关注,被认为是调控光催化材料性能的有效途径之一。自2008年yang等首次合成高表面能{001}晶面占优的锐钛矿TiO2单晶以来,控制合成暴露不同晶面TiO2晶体的研究得到了迅猛的发展,已发展了多种方法合成了具有不同晶面的TiO2晶体。研究表明,选择性地暴露特定的活性晶面能够显著地提高光催化剂的活性或者改变光催化反应的选择性。但是,含有完整晶面构型的TiO2单晶样品的颗粒尺寸一般都较大,通常为几微米,因而显著增加了光生载流子传输与分离的难度,并且导致材料较小的比表面积,限制了对光催化活性的进一步提高。能否在合成含特定晶面单晶的同时增加多孔结构成为有效解决这一问题的关键。最近, Crossland等采用晶种模板法成功合成了介孔的锐钛矿TiO2单晶,并且通过光电器件研究证实了采用该思路可进一步提高材料的光电性能。金红石TiO2在光催化全分解水方面具有独特的优势,然而关于多孔单晶金红石TiO2的研究相对较少,尤其是合成热力学不稳定的高表面能{111}晶面完全暴露的多孔金红石单晶面临较大的技术挑战因而一直未见文献报道。本文利用晶种模板法,以TiCl4溶液为含Ti前驱体、NaF为形貌控制剂、采用水热处理制备出不同比例{111}晶面的介孔金红石单晶。我们前期工作表明, NaF可作为形貌控制剂合成低表面能{110)晶面占优的介孔金红石单晶。本文发现,通过改变NaF的添加量,可有效调变{111}/{110}晶面比例,最终合成完全暴露{111}高表面能的介孔金红石TiO2单晶。扫描电镜结果显示,当添加20 mg NaF时,合成{110}占优的具有高长径比的介孔晶体;当NaF用量增加到40 mg时{110}晶面进一步缩短;至80 mg时则制备出{111})高能面完全暴露的金红石TiO2晶体。值得注意的是,对比研究表明,不采用模板合成了与多孔晶体完全相对应的不同{111}/(110}晶面比例的实心金红石晶体。透射电镜及选区电子衍射以及结合X射线衍射进一步证实,多孔的金红石TiO2晶体与实心金红石单晶均都为单晶结构,孔结构贯穿于样品内部且具有较高的晶面结晶性。氮气吸附实验发现,虽然三个不同晶面比例介孔金红石单晶样品间的形貌具有显著的差异,但比表面积非常相近(分别为24,25,28 m2/g),孔径也都为50 nm左右,该值与所用SiO2模板球的直径以及TEM观察结果相一致。光催化产氢性能结果表明,选择性的暴露活性晶面显著提高了光催化活性,仅含高能面{111}的介孔金红石单晶样品具有最高的产氢速率(约800μmol h–1 g–1),比常规{110}晶面占优的介孔单晶样品速率提高了约一倍。尤其比实心单晶样品的产氢速率提高了至少一个数量级,这应归结于介孔结构特性所导致的表面反应活性位增加、电子传输距离缩短以及光吸收增强协同作用的结果。     

八面体结构ZnGa2O4微晶的制备及其光催化性能

以乙酸锌和氧化镓为反应原料,以乙二胺四乙酸(EDTA)为配位剂,采用溶胶-凝胶法制备了八面体结构的ZnGa2O4微晶。通过TG-DSC,XRD、SEM等分析方法对ZnGa2O4微晶进行了测试和表征。研究了其物相组成、显微结构、形成机理及光催化性能。结果表明,在700℃、4～6 h时可以成功制备出八面体结构的ZnGa2O4单晶,其暴露的晶面族{111};八面体结构ZnGa2O4的合成是一个受ZnO的产生速率所控制的过程;光催化降解罗丹明B的实验表明,八面体结构ZnGa2O4微晶有着较好的光催化性能。     

CO氧化反应中的二氧化铈晶面效应

二氧化铈(CeO2)因其具有较强的储放氧能力,被用作氧化还原反应的催化材料.自2005年,研究者制备出形貌可控的CeO2纳米棒、纳米立方块和纳米多面体,在CeO2形貌控制及构效关系研究方面取得长足发展.各种结构表征手段包括原位拉曼(in situ Raman)、原位傅里叶变换红外光谱(in situ DRIFTS)、核磁共振(NMR)和电镜等被用来研究不同形貌CeO2的表面结构和在催化反应中的活性差异.一般的活性规律为CeO2纳米棒({110}/{100})>纳米立方块({100})>纳米多面体({111}/{100}).近年来,负载型CeO2催化剂因其能稳定分散金属,通过金属-载体相互作用调控界面电子结构并表现出优异的催化活性而引起广泛关注,其中晶面效应在负载型CeO2催化体系中显得较为复杂.铜铈催化剂被认为是非常经济有效的CO氧化催化剂,然而由于制备和测试条件差异导致的CeO2晶面对铜铈催化剂催化CO氧化活性的影响规律并不统一.我们之前的研究工作发现纳米棒CeO2-{110}晶面上的Cu-[Ox]-Ce结构不利于形成Cu((40)),而纳米颗粒CeO2-{111}晶面上的CuOx团簇很容易形成Cu((40)),从而对CO催化氧化极为有利,这与纯载体CeO2的规律并不一致.与此同时,对于铜负载的CeO2纳米棒(NR)及纳米立方体(NC)所体现的性质及活性差异缺少系统深入的研究.在上述工作基础上,我们采用沉积沉淀法在CeO2 NR及CeO2 NC上负载1%wt的铜分别得到1Cu CeNR和1Cu CeNC,并对所合成催化剂的结构和吸附性能进行了表征.高分辨透射电镜(HRTEM)照片显示,CeO2纳米棒主要暴露{110}晶面,而CeO2纳米立方体以{100}晶面为主.催化测试结果表明,1Cu CeNC在130℃时CO已完全转化为CO2,而相同温度下1Cu Ce NR只有50%转化.进一步通过氢气程序升温还原(H2-TPR)和一氧化碳程序升温脱附(CO-TPD)分析发现, 1Cu Ce NC催化剂具有较强的还原性且表面氧物种含量高.此外, X射线光电子能谱(XPS)和in situ DRIFTS研究表明, 1Cu Ce NC促进Cu((40))位点生成,导致活性Cu((40))-CO物种增多,这些优异的化学性质导致其具有较高的催化CO氧化活性.     

CO氧化反应中的二氧化铈晶面效应（英文）

二氧化铈(CeO_2)因其具有较强的储放氧能力,被用作氧化还原反应的催化材料.自2005年,研究者制备出形貌可控的CeO_2纳米棒、纳米立方块和纳米多面体,在CeO_2形貌控制及构效关系研究方面取得长足发展.各种结构表征手段包括原位拉曼(in situ Raman)、原位傅里叶变换红外光谱(in situ DRIFTS)、核磁共振(NMR)和电镜等被用来研究不同形貌CeO_2的表面结构和在催化反应中的活性差异.一般的活性规律为CeO_2纳米棒({110}/{100})纳米立方块({100})纳米多面体({111}/{100}).近年来,负载型CeO_2催化剂因其能稳定分散金属,通过金属-载体相互作用调控界面电子结构并表现出优异的催化活性而引起广泛关注,其中晶面效应在负载型CeO_2催化体系中显得较为复杂.铜铈催化剂被认为是非常经济有效的CO氧化催化剂,然而由于制备和测试条件差异导致的CeO_2晶面对铜铈催化剂催化CO氧化活性的影响规律并不统一.我们之前的研究工作发现纳米棒CeO_2-{110}晶面上的Cu-[O_x]-Ce结构不利于形成Cu((40)),而纳米颗粒CeO_2-{111}晶面上的CuO_x团簇很容易形成Cu((40)),从而对CO催化氧化极为有利,这与纯载体CeO_2的规律并不一致.与此同时,对于铜负载的CeO_2纳米棒(NR)及纳米立方体(NC)所体现的性质及活性差异缺少系统深入的研究.在上述工作基础上,我们采用沉积沉淀法在CeO_2 NR及CeO_2 NC上负载1%wt的铜分别得到1Cu CeNR和1Cu CeNC,并对所合成催化剂的结构和吸附性能进行了表征.高分辨透射电镜(HRTEM)照片显示,CeO_2纳米棒主要暴露{110}晶面,而CeO_2纳米立方体以{100}晶面为主.催化测试结果表明,1Cu CeNC在130°C时CO已完全转化为CO2,而相同温度下1Cu Ce NR只有50%转化.进一步通过氢气程序升温还原(H2-TPR)和一氧化碳程序升温脱附(CO-TPD)分析发现, 1Cu Ce NC催化剂具有较强的还原性且表面氧物种含量高.此外, X射线光电子能谱(XPS)和in situ DRIFTS研究表明, 1Cu Ce NC促进Cu((40))位点生成,导致活性Cu((40))-CO物种增多,这些优异的化学性质导致其具有较高的催化CO氧化活性.     

从头开始理解形貌依赖的CuOx-CeO_2相互作用（英文）

CuO_x/CeO_2催化剂在CO氧化反应中表现出高催化活性和显著结构敏感性.文献报道中CuO_x/CeO_2催化剂体系的合成条件差异较大,从而导致观察到的CuO_x-CeO_2相互作用存在较大争议.因此,系统研究并阐明CuO_x/CeO_2催化剂中CuO_x-CeO_2相互作用对于理解复杂的CuO_x-CeO_2界面催化作用具有重要的研究意义.近期发现,氧化物纳米晶的形貌可作为一种新的结构参数,在不改变氧化物催化剂组成的条件下实现其结构和性能的调控.本文以不同形貌CeO_2纳米晶为载体,包括优先暴露{110}+{100}晶面的CeO_2纳米棒、优先暴露{100}晶面的CeO_2纳米立方体和优先暴露{111}晶面的CeO_2纳米多面体,采用等体积浸渍方法合成了Cu担载量为0.025%～5%的CuO_x/CeO_2纳米晶催化剂,结合谱学和电镜表征方法,以及CO吸附原位红外光谱,系统研究了CuO_x物种在不同形貌CeO_2纳米晶上的结构演化及其催化CO氧化的构-效关系.结构表征结果表明, CuO_x物种结构不仅依赖于Cu的担载量,也依赖于载体CeO_2的形貌.随着Cu担载量的增加, CuO_x物种优先沉积在CeO_2的表面缺陷位,然后聚集和长大;同时伴随着CuO_x物种从孤立Cu离子到与载体强/弱相互作用的CuO_x团簇,高分散Cu O颗粒和大尺寸Cu O颗粒.孤立Cu+离子和与载体弱相互作用CuO_x团簇主要形成于CeO_2纳米立方体的表面,这可能与CeO_2纳米立方体暴露的氧终止CeO_2{100}晶面相关.CO吸附原位红外结果表明, CuO_x团簇与不同CeO_2表面相互作用的强度顺序为:CeO_2纳米棒暴露的{110}面CeO_2纳米多面体暴露的{111}面CeO_2纳米立方体暴露的{100}面.CeO_2纳米立方体与Cu2+离子间相互作用弱于与Cu+之间的,因此CeO_2纳米立方体负载的CuO_x物种在CO还原过程中容易停留在稳定的Cu+中间物种;而CeO_2纳米棒与Cu2+离子之间的相互作用强于与Cu+之间的相互作用,因此CeO_2纳米棒负载的CuO_x物种在CO还原过程中容易形成金属铜.因此CO吸附原位红外光谱观察到CeO_2纳米立方体负载CuO_x催化剂中吸附在Cu+的CO物种远远多于CeO_2纳米棒负载CuO_x催化剂.CO氧化反应结果表明, CuO_x/CeO_2催化剂表现出同时依赖于CuO_x物种结构和CeO_2形貌的结构敏感性.CuO_x/CeO_2催化剂活性表现出与CuO_x/CeO_2催化剂的CO还原性能的正相关性,说明中CuO_x/CeO_2催化CO氧化反应遵循Mv K反应机理.这些结果系统地关联了CeO_2形貌, CuO_x-CeO_2相互作用, CuO_x物种结构和CeO_2还原性能, CuO_x/CeO_2催化CO氧化反应活性.     

α-Fe2O3表面结构对NH3选择性催化还原NO活性的影响

通过水热法合成了两种具有不同形貌的α-Fe2O3纳米棒和纳米立方体,并探索了它们的中温NH3选择性催化还原(NH3-SCR)NO的活性.NH3-SCR测试表明α-Fe2O3纳米棒具有更高的催化活性.X射线粉末衍射(XRD)、场发射扫描电镜(FE-SEM)和高分辨透射电镜(HRTEM)结构分析表明:α-Fe2O3纳米棒暴露有高表面能的{110}活性面,而纳米立方体暴露的主要是低表面能的{012}晶面.H2程序升温还原(H2-TPR)和NO程序升温脱附(NO-TPD)结果证明纳米棒比纳米立方体具有更高的氧化还原性能.因此,α-Fe2O3纳米棒由于暴露高表面能的活性面具有比纳米立方体更高的NH3-SCR性能.     

从头开始理解形貌依赖的CuOx-CeO2相互作用

CuOx/CeO2催化剂在CO氧化反应中表现出高催化活性和显著结构敏感性.文献报道中CuOx/CeO2催化剂体系的合成条件差异较大,从而导致观察到的CuOx-CeO2相互作用存在较大争议.因此,系统研究并阐明CuOx/CeO2催化剂中CuOx-CeO2相互作用对于理解复杂的CuOx-CeO2界面催化作用具有重要的研究意义.近期发现,氧化物纳米晶的形貌可作为一种新的结构参数,在不改变氧化物催化剂组成的条件下实现其结构和性能的调控.本文以不同形貌CeO2纳米晶为载体,包括优先暴露{110}+{100}晶面的CeO2纳米棒、优先暴露{100}晶面的CeO2纳米立方体和优先暴露{111}晶面的CeO2纳米多面体,采用等体积浸渍方法合成了Cu担载量为0.025%~5%的CuOx/CeO2纳米晶催化剂,结合谱学和电镜表征方法,以及CO吸附原位红外光谱,系统研究了CuOx物种在不同形貌CeO2纳米晶上的结构演化及其催化CO氧化的构-效关系.结构表征结果表明, CuOx物种结构不仅依赖于Cu的担载量,也依赖于载体CeO2的形貌.随着Cu担载量的增加, CuOx物种优先沉积在CeO2的表面缺陷位,然后聚集和长大;同时伴随着CuOx物种从孤立Cu离子到与载体强/弱相互作用的CuOx团簇,高分散Cu O颗粒和大尺寸Cu O颗粒.孤立Cu^+离子和与载体弱相互作用CuOx团簇主要形成于CeO2纳米立方体的表面,这可能与CeO2纳米立方体暴露的氧终止CeO2{100}晶面相关.CO吸附原位红外结果表明, CuOx团簇与不同CeO2表面相互作用的强度顺序为:CeO2纳米棒暴露的{110}面>CeO2纳米多面体暴露的{111}面>CeO2纳米立方体暴露的{100}面.CeO2纳米立方体与Cu2+离子间相互作用弱于与Cu^+之间的,因此CeO2纳米立方体负载的CuOx物种在CO还原过程中容易停留在稳定的Cu^+中间物种;而CeO2纳米棒与Cu2+离子之间的相互作用强于与Cu^+之间的相互作用,因此CeO2纳米棒负载的CuOx物种在CO还原过程中容易形成金属铜.因此CO吸附原位红外光谱观察到CeO2纳米立方体负载CuOx催化剂中吸附在Cu^+的CO物种远远多于CeO2纳米棒负载CuOx催化剂.CO氧化反应结果表明, CuOx/CeO2催化剂表现出同时依赖于CuOx物种结构和CeO2形貌的结构敏感性.CuOx/CeO2催化剂活性表现出与CuOx/CeO2催化剂的CO还原性能的正相关性,说明中CuOx/CeO2催化CO氧化反应遵循Mv K反应机理.这些结果系统地关联了CeO2形貌, CuOx-CeO2相互作用, CuOx物种结构和CeO2还原性能, CuOx/CeO2催化CO氧化反应活性.     

铜-氧化铈界面:几何及电子结构（英文）

纳米催化材料的性能主要由粒子尺寸、形貌和界面决定,即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究,即催化剂的构效关系,一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能, Cu/CeO_2催化剂在CO氧化、N_2O消除、水气变换、甲醇合成等反应中表现出优异性能.其中,通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种,而铜物种促进氧化铈的氧化还原能力,涉及Cu~(2+)/Cu~+/Cu~0和Ce~(3+)/Ce~(4+)之间电子的传输和转移.Cu/CeO_2催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子(多面体)、纳米棒和纳米立方体,可分别选择性暴露(111)、(110)和(100)晶面;这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比,主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度,也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态;随着铜负载量的增加,可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下,低负载量有利于单层、双层铜物种的形成,高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生,与氧化铈表面氧空穴的数量和密度密切相关,即氧化铈形貌.本文总结了Cu/CeO_2催化剂的研究进展,讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律,总结了铜氧化铈界面结构的多维度表征结果,比较了Cu/CeO_2催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.     

Morphological evolution of Cu2O nanocrystals in an acid solution: stability of different crystal planes

The morphological evolution of uniform Cu(2)O nanocrystals with different morphologies in a weak acetic acid solution (pH = 3.5) has been studied for cubic, octahedral, rhombic dodecahedral, {100} truncated octahedral, and {110} truncated octahedral nanocrystals. Cu(2)O nanocrystals undergo oxidative dissolution in weak acid solution, but their morphological changes depend on the exposed crystal planes. We found that the stability of Cu(2)O crystal planes in weak acid solution follows the order of {100} ? {111} > {110} and determines how the morphology of Cu(2)O nanocrystals evolves. The stable {100} crystal planes remain, and new {100} facets form at the expense of the less stable {111} and {110} crystal planes on the surface of Cu(2)O nanocrystals. Density functional theory calculations reveal that the Cu-O bond on Cu(2)O(100) surface has the shortest bond length. These results clearly exemplify that the morphology of inorganic crystals will evolve with the change of local chemical environment, shedding light on fundamentally understanding the morphological evolution of natural minerals and providing novel insights into the geomimetic synthesis of inorganic materials in the laboratory.     

Facet‐Dependent Catalytic Activity of Cu2O Nanocrystals in the One‐Pot Synthesis of 1,2,3‐Triazoles by Multicomponent Click Reactions

We report the highly facet‐dependent catalytic activity of Cu₂O nanocubes, octahedra, and rhombic dodecahedra for the multicomponent direct synthesis of 1,2,3‐triazoles from the reaction of alkynes, organic halides, and NaN₃. The catalytic activities of clean surfactant‐removed Cu₂O nanocrystals with the same total surface area were compared. Rhombic dodecahedral Cu₂O nanocrystals bounded by {110} facets were much more catalytically active than Cu₂O octahedra exposing {111} facets, whereas Cu₂O nanocubes displayed the slowest catalytic activity. The superior catalytic activity of Cu₂O rhombic dodecahedra is attributed to the fully exposed surface Cu atoms on the {110} facet. A large series of 1,4‐disubstituted 1,2,3‐triazoles have been synthesized in excellent yields with high regioselectivity under green conditions by using these rhombic dodecahedral Cu₂O catalysts, including the synthesis of rufinamide, an antiepileptic drug, demonstrating the potential of these nanocrystals as promising heterogeneous catalysts for other important coupling reactions.     

Synthesis of Cu2O nanocrystals from cubic to rhombic dodecahedral structures and their comparative photocatalytic activity

In this study, a new series of Cu(2)O nanocrystals with systematic shape evolution from cubic to face-raised cubic, edge- and corner-truncated octahedral, all-corner-truncated rhombic dodecahedral, {100}-truncated rhombic dodecahedral, and rhombic dodecahedral structures have been synthesized. The average sizes for the cubes, edge- and corner-truncated octahedra, {100}-truncated rhombic dodecahedra, and rhombic dodecahedra are approximately 200, 140, 270, and 290 nm, respectively. An aqueous mixture of CuCl(2), sodium dodecyl sulfate, NaOH, and NH(2)OH·HCl was prepared to produce these nanocrystals at room temperature. Simple adjustment of the amounts of NH(2)OH·HCl introduced enables this particle shape evolution. These novel particle morphologies have been carefully analyzed by transmission electron microscopy (TEM). The solution color changes quickly from blue to green, yellow, and then orange within 1 min of reaction in the formation of nanocubes, while such color change takes 10-20 min in the growth of rhombic dodecahedra. TEM examination confirmed the rapid production of nanocubes and a substantially slower growth rate for the rhombic dodecahedra. The rhombic dodecahedra exposing only the {110} facets exhibit an exceptionally good photocatalytic activity toward the fast and complete photodegradation of methyl orange due to a high number density of surface copper atoms, demonstrating the importance of their successful preparation. They may serve as effective and cheap catalysts for other photocatalytic reactions and organic coupling reactions.     

Crystal‐Plane‐Controlled Selectivity of Cu2O Catalysts in Propylene Oxidation with Molecular Oxygen

The selective oxidation of propylene with O₂ to propylene oxide and acrolein is of great interest and importance. We report the crystal‐plane‐controlled selectivity of uniform capping‐ligand‐free Cu₂O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O₂: Cu₂O octahedra exposing {111} crystal planes are most selective for acrolein; Cu₂O cubes exposing {100} crystal planes are most selective for CO₂; Cu₂O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One‐coordinated Cu on Cu₂O(111), three‐coordinated O on Cu₂O(110), and two‐coordinated O on Cu₂O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO₂, respectively. These results reveal that crystal‐plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level.     

Hydrothermal Synthesis and Structure of a Mixed-valence Polyoxotungstate Decorated by Copper(I) Coordination Group, [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]·2H2O

A complex [Cu(en)2H2O]2[{Cu(en)2}HPW12O40]·2H2O (C12H57Cu3N12O44PW12, Mr = 3501.49) has been synthesized under hydrothermal conditions and its crystal structure was determined by X-ray diffraction.It crystallizes in the orthorhombic system, space group Pbca with a = 21.680(4), b = 20.680(4), c = 26.120(5) (A), V = 11711(4) (A)3, Dc = 3.972 g/cm3, Z = 8, μ(MoKa) = 24.661 mm-1, F(000) = 12440, the final R = 0.0527 and wR = 0.1416 for 11527 observed reflec- tions with I > 2σ(I).The crystal structure is composed of [{Cu(en)2}HPW12O40]2- anions, discrete [Cu(en)2H2O]+ complex cations and crystal water molecules, which are held together into a three- dimensional network through hydrogen-bonding interactions.The anionic [{Cu(en)2}HPW12O40]2- is formed by the mixed valance {HPWVI11WVO40}3- Keggin unit covalently linked by a {Cu(en)2}+ group.     

Fabrication of truncated rhombic dodecahedral Cu2O nanocages and nanoframes by particle aggregation and acidic etching

We report a simple approach for the fabrication of cuprous oxide (Cu 2O) nanocages and nanoframes possessing an unusual truncated rhombic dodecahedral structure. An aqueous solution containing CuCl 2, sodium dodecyl sulfate (SDS) surfactant, NH 2OH.HCl reductant, HCl, and NaOH was prepared, with the reagents introduced in the order listed. Rapid seed-particle aggregation and surface reconstruction of the intermediate structure resulted in the growth of type-I nanoframes, which have only {110} skeleton faces and empty {100} faces, 45 min after mixing the reagents. Continued crystal growth for additional 75 min produced nanocages with filled {100} faces. The nanocages have diameters of 350-400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol followed by sonication of the solution led to the formation of type-II nanoframes, which have elliptical pores on the {110} faces. The morphologies of these nanoframes were carefully examined by electron microscopy. Without addition of ethanol, random etching of the nanocages can occur at a slow rate. Octahedral gold nanocrystals and high-aspect-ratio gold nanorods were successfully encapsulated in the interiors of these Cu 2O nanocages by adding the gold nanostructures into the reaction solution. The formation process for such core-cage composite structures was studied. These composite materials should display interesting properties and functions.     

Facet effect of single-crystalline Ag3PO4 sub-microcrystals on photocatalytic properties

We recently reported that Ag(3)PO(4) exhibits excellent photooxidative capabilities for O(2) evolution from water and organic dye decomposition under visible-light irradiation. However, very little is known about the shape and facet effects of Ag(3)PO(4) crystals on their photocatalytic properties. Herein we have developed a facile and general route for high-yield fabrication of single-crystalline Ag(3)PO(4) rhombic dodecahedrons with only {110} facets exposed and cubes bounded entirely by {100} facets. Moreover, studies of their photocatalytic performance have indicated that rhombic dodecahedrons exhibit much higher activities than cubes for the degradation of organic contaminants, which may be primarily ascribed to the higher surface energy of {110} facets (1.31 J/m(2)) than of {100} facets (1.12 J/m(2)).     

Highly Facet‐Dependent Photocatalytic Properties of Cu2O Crystals Established through the Formation of Au‐Decorated Cu2O Heterostructures

This work confirms the presence of a large facet‐dependent photocatalytic activity of Cu₂O crystals through sparse deposition of gold particles on Cu₂O cubes, octahedra, and rhombic dodecahedra. Au‐decorated Cu₂O rhombic dodecahedra and octahedra showed greatly enhanced photodegradation rates of methyl orange resulting from a better separation of the photogenerated electrons and holes, with the rhombic dodecahedra giving the best efficiency. Au–Cu₂O core–shell rhombic dodecahedra also displayed a better photocatalytic activity than pristine rhombic dodecahedra. However, Au‐deposited Cu₂O cubes, pristine cubes, and Au‐deposited small nanocubes bound by entirely {100} facets are all photocatalytically inactive. X‐ray photoelectron spectra (XPS) showed identical copper peak positions for these Au‐decorated crystals. Remarkably, electron paramagnetic resonance (EPR) measurements indicated a higher production of hydroxyl radicals for the photoirradiated Cu₂O rhombic dodecahedra than for the octahedra, but no radicals were produced from photoirradiated Cu₂O cubes. The Cu₂O {100} face may present a high energy barrier through its large band edge bending and/or electrostatic repulsion, preventing charge carriers from reaching to this surface. The conventional photocatalysis model fails in this case. The facet‐dependent photocatalytic differences should be observable in other semiconductor systems whenever a photoinduced charge‐transfer process occurs across an interface.     

0-aminophenol and 8-hydroxyquinoline as ligands of Cu(II) in 1M-Na(ClO4) at 25°C

The complex formation between Cu(II) and 8-hydroxyquinolinat (Ox) was studied with the liquid-liquid distribution method, between 1M-Na(ClO₄) and CHCl₃ at 25°C. The experimental data were explained by the equilibria: $$\begin{gathered} \operatorname{Cu} ^{2 + } + Ox \rightleftharpoons \operatorname{Cu} Ox \log \beta _1 = 12.38 \pm 0.13 \hfill \\ \operatorname{Cu} ^{2 + } + 2 Ox \rightleftharpoons \operatorname{Cu} Ox_2 \log \beta _2 = 23.80 \pm 0.10 \hfill \\ \operatorname{Cu} Ox_{2aq} \rightleftharpoons \operatorname{Cu} Ox_{2\operatorname{org} } \log \lambda = 2.06 \pm 0.08 \hfill \\ \end{gathered} $$ The equilibria between Cu(II) and o-aminophenolate (AF) were studied potentiometrically with a glass electrode at 25°C and in 1M-Na(ClO₄). The experimental data were explained by the equilibria: $$\begin{gathered} \operatorname{Cu} ^{2 + } + AF \rightleftharpoons \operatorname{Cu} AF \log \beta _1 = 8.08 \pm 0.08 \hfill \\ \operatorname{Cu} ^{2 + } + 2AF \rightleftharpoons \operatorname{Cu} AF_2 \log \beta _2 = 14.60 \pm 0.06 \hfill \\ \end{gathered} $$ The protonation constants ofAF and the distribution constants between CHCl₃?H₂O and (C₂H₅)₂O?H₂O were also determined.     

Solid state coordination chemistry of metal oxides: structural consequences of fluoride incorporation into the oxovanadium-copper-bisterpy-{O3P(CH2)nPO3}4- system, n= 1-5 (bisterpy = 2,2':4',4":2",2"'-quaterpyridyl-6', 6"-di-2-pyridine)

Hydrothermal reactions of a vanadate source, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2(n= 1-5), in the presence of HF, yielded a family of materials of the type oxyfluorovanadium/copper-bisterpy/organodiphosphonate. Under similar reaction conditions, variations in diphosphonate tether length n provided the one-dimensional [{Cu2(bisterpy)}V2F2O2{HO3PCH2PO3}{O3PCH2PO3}](1) and [{Cu2(bisterpy)}V2F4O4{HO3P(CH2)2PO3H}](3), the two-dimensional [{Cu2(bisterpy)}V2F2O2(H2O)2{HO3P(CH2)2PO3}2] x 2H2O (2 x 2H2O), [{Cu2(bisterpy)(H2O2}V2F2O2{O3P(CH2)3PO3}{HO3P(CH2)3PO3H}(4) and [{Cu2(bisterpy)}V4F4O4(OH)(H2O){HO3P(CH2)5PO3}{O3P(CH2)5PO3}] x H2O (9 x H2O) and the three-dimensional [{Cu2(bisterpy)}3V8F6O17{HO3P(CH2)3PO3}4]0.8H2O (5 x 0.8H2O), [{Cu2(bisterpy)}V4F2O6{O3P(CH2)4PO3}2](8) and [{Cu2(bisterpy)(H2O)}2V8F4O8(OH)4{HO3P(CH2)5PO3H}2{O3P(CH2)5PO)}3] x 4.8H2O (10 x 4.8H2O). In addition, two members of the oxovanadium/Cu2(bisterpy)/organodiphosphonate family [{Cu2(bisterpy)}V2O4{HO3P(CH2)3PO3}2](6) and [{Cu2(bisterpy)}3V4O8(OH)2{O3P(CH2)3PO3}2{HO3P(CH2)3PO3}2] x 5H2O (7 x 5H2O) cocrystallized from the reaction mixture which provided 5. The overall architectures reveal embedded substructures based on V/P/O(F) clusters, chains, networks, and frameworks. In contrast to the oxovanadium/Cu2(bisterpy)/ organodiphosphonate family, several of the materials of this study also exhibit the direct condensation of vanadium polyhedra to produce binuclear and/or tetranuclear building units.