SnCl_(2)促进的Pt1/PS-PPh_(2)催化剂高选择性催化高碳烯烃氢甲酰化反应

PS‐PPh_(2) tethered Pt single atoms promoted by SnCl_(2) as highly efficient and regio‐selective catalysts for the hydroformylation of higherα‐alkenes

氢甲酰化作为工业上制备醛、醇等含氧化合物的重要反应,广泛应用于制备洗涤剂、增塑剂、表面活性剂和香料等.目前,氢甲酰化反应主要使用HCo(CO)_(4),HCo(CO)_(3)(PR_(3))和HRh(CO)(PPh_(3))_(2)等配合物作为催化剂.尽管Co基催化剂可以将高碳烯烃、内烯烃以及支链烯烃高选择性地转化为直链醛,但其反应条件(5-30 MPa,140-200℃)较苛刻,且容易发生烯烃加氢等副反应.相比之下,Rh催化剂的活性比Co基催化剂高1-2个数量级,且反应条件较为温和.但Rh储量稀少,价格昂贵,而且对于高碳烯烃氢甲酰化反应,Rh催化剂难以分离和循环使用.因此,研究者开展了其他金属催化剂的研究,其中Pt-Sn催化剂因其出色的区域选择性而备受关注.但目前Pt-Sn催化剂多局限于均相催化体系,而且Sn助剂的作用尚不明确.本文采用商业化三苯基膦嫁接的聚苯乙烯小球为载体,通过浸渍法制备了SnCl_(2)-Pt_(1)/PS-PPh_(2)单原子催化剂,考察了其在长链-烯烃氢甲酰化反应中的催化性能,并研究了Sn的促进作用.首先,以1-己烯氢甲酰化为探针反应,对催化剂的组成以及反应条件进行了优化.当Pt/P/Sn=1/2/5时,催化剂表现出最高的催化活性,在90-120℃和4-6 MPa合成气条件下,催化剂转化频率(TOF)为40 h^(-1),产物醛的正异比>42.随后,考察了催化剂的底物适用性.结果表明,C6-C12的高碳烯烃均可被高选择性地转化为相应的醛(正异比>20).然而,在循环使用实验中,由于SnCl_(2)不能稳定锚定在载体上,第二次循环时催化活性降低.但通过补加SnCl_(2),催化活性可以完全恢复.高压热过滤实验及元素检测结果表明,反应过程中Pt没有流失.X射线吸收光谱(XAFS)表征结果表明,反应后Pt仍以单原子形式存在,说明Pt1/PS-PPh_(2)具有良好的稳定性.通过准原位X-射线吸收谱、Mössbauer谱和红外光谱表征对反应过程中Pt和Sn的电子性质和配位结构进行了研究.结果表明,SnCl_(2)在反应过程中逐渐转化为Sn(dioxane)Cl3-物种(1,4-二氧六环为反应溶剂),并与Pt原子形成Pt-Sn键.当反应体系中没有Sn时,Pt(II)会被合成气过度还原并发生团聚.当没有膦配体时,Pt原子也会发生聚集,而且SnCl_(2)会在Pt(II)的催化作用下发生水解生成SnO.因此Sn(dioxane)Cl3-与膦配体共同抑制了Pt(I)在反应过程中的还原与聚集.最后,通过XAFS表征深入研究了反应机理.分析结果表明,CO在催化剂上具有较强的吸附作用,而H_(2)则可能以异裂的方式在催化剂上被活化.据此提出可能的反应机理:首先,H_(2)在催化剂上活化先形成Pt-H物种;随后,烯烃插入Pt-H,形成Pt-烷基物种;接着,CO迁移并插入,生成Pt-酰基物种;最后,经过还原消除步骤,得到最终的产物醛.综上,本文制备了一种对高碳烯烃氢甲酰化反应具有良好催化性能的SnCl_(2)-Pt1/PS-PPh_(2)单原子催化剂,为低成本非Rh基催化剂的开发提供借鉴.同时,揭示了催化体系中Sn的促进作用,为通过Lewis酸来调控催化剂的性能提供了参考.

Rh-P complexes have been widely used as catalysts for hydroformylation reactions.The extremely high price of Rh and its scarce reserves have prompted the exploration of the alternatives.In this study,we reported that Pt/PS-PPh_(2) single-atom catalysts promoted by SnCl_(2) were highly efficient and selective for the hydroformylation of higherα-alkenes.A broad scope of substrates(i.e.,C_(6)-C_(12))were smoothly converted to the corresponding linear aldehydes with high yields under reaction conditions of 90-120℃ and 4-6 MPa syngas.The turnover frequency(TOF)was comparable to homogeneous Pt-Sn catalysts,and the linear/branched ratio reached as high as>20.In addition,the catalyst could be reused with the extra addition of SnCl_(2).The promotional role of SnCl_(2) was elucidated by quasi-in situ X-ray adsorption fine structure,Fourier transform infrared,and Mössbauer spectroscopy.It was discovered that SnCl_(2) was transformed into Sn(dioxane)Cl3-species coordinated to Pt as a moderately electron-donating ligand,which,together with the phosphine group,stabilized mononuclear Pt(I)species against reduction and aggregation.