类水滑石Mg_3Al_(1–x)Fe_x负载Ir催化剂在肉桂醛加氢反应中的应用:Fe的促进作用（英文）

Layered double hydroxide-like Mg_3Al_(1–x)Fe_x materials as supports for Ir catalysts: Promotional effects of Fe doping in selective hydrogenation of cinnamaldehyde

摘要:水滑石类化合物(LDH)的层板金属阳离子组成具有可调变性,通过将具有变价特性的过渡金属定量引入LDH层板,经热处理后可以得到具有高比表面积和层板金属原子级分散的混合金属氧化物,后者可广泛用作催化剂载体.如三元Mg-Al-Fe类水滑石材料在光催化、H_2S选择性氧化和乙苯脱氢等反应中表现出较好的活性.Ir催化剂在α,β-不饱和醛加氢反应中具有较好的活性,Fe修饰Ir催化剂可提高不饱和醇选择性,但有关Fe的作用以及Fe与活性组分Ir间的相互作用本质还不是很清楚.本文以类水滑石材料Mg_3Al_(1–x)Fe_x为载体,采用等体积浸渍法制备了Ir催化剂,并用于肉桂醛加氢反应,通过考察Fe的加入对Ir电子和几何结构的影响揭示了Fe的加入对活性和选择性的影响规律.结果表明,当x从0(Ir/Mg_3Al)增加到1(Ir/Mg_3Fe)时,肉桂醛加氢的反应速率在x=0.25时达到最大值,肉桂醇选择性从44.9%增加到80.3%,且不随肉桂醛转化率的增加而改变.透射电镜结果表明,Ir纳米粒子的粒径随着x的增加未发生明显变化,均为1.7?0.2 nm.H_2程序升温还原结果发现Ir可以促进Fe^(3+)的还原且两者之间存在相互作用.X射线光电子能谱结果表明,Fe的掺杂没有改变催化剂表面Ir^0和Ir^(4+)含量的比值,但当Fe含量增加时,Fe^(2+)2p_(3/2)向高结合能方向偏移,且Ir^04f_(7/2)向低结合能方向偏移,说明电子从Fe^(2+)转移到Ir,形成了富电子的Ir物种和缺电子的Fe物种.富电子的Ir物种有利于肉桂醛分子中的C=O键在其表面吸附,并且和Ir相邻的Fe^(n+)物种可以作为亲电位点吸附肉桂醛分子中氧,从而极化和活化C=O键,因而催化剂活性和选择性增大.采用吸附CO红外光谱表征了催化剂表面的几何结构,2058–2069 cm^(-1)处出现了CO吸附峰,归属于Ir^0表面CO的线性吸附,高波数2069 cm^(-1)的吸附峰归属于CO在高配位Ir位点(平台)的吸附,低波数2058 cm^(-1)的吸附峰归属于CO在低配位Ir位点(台阶、角、楞)的吸附.随着Fe含量的增加,CO吸附峰蓝移11 cm^(-1),表明Fe的加入改变了催化剂表面Ir的几何结构,低配位Ir位点减少,高配位Ir位点增多.高配位Ir位点(平台)有利于肉桂醛分子中C=O键的吸附,从而提高了肉桂醇的选择性.总之,Fe的加入虽然没有明显改变Ir纳米粒子的粒径,但却改变了其电子和几何结构,从而提高了催化剂活性和选择性.

Supported Ir catalysts were prepared using layered double hydrotalcite‐like materials,such as Mg3Al1-xFex,containing Fe and Al species in varying amounts as supports.These Ir catalysts were applied for the selective hydrogenation of cinnamaldehyde(CAL).When x was changed from 0(Ir/Mg3Al)to 1(Ir/Mg3Fe),the rate of CAL hydrogenation reached a maximum at approximately x=0.25,while the selectivity to unsaturated alcohol,i.e.,cinnamyl alcohol,monotonously increased from 44.9%to 80.3%.Meanwhile,the size of the supported Ir particles did not change significantly with x,remaining at 1.7-0.2 nm,as determined by transmission electron microscopy.The chemical state of Ir and Fe species in the Ir/Mg3Al1-xFex catalysts was examined by temperature programmed reduction by H2 and X‐ray photoelectron spectroscopy.The surface of the supported Ir particles was also examined through the in‐situ diffuse reflectance infrared Fourier‐transform of a probe molecule of CO.On the basis of these characterization results,the effects of Fe doping to Mg3Al on the structural and catalytic properties of Ir particles in selective CAL hydrogenation were discussed.The significant factors are the electron transfer from Fe2+in the Mg3Al1–xFex support to the dispersed Ir particles and the surface geometry.