一种钍-铁金属氧簇的合成、结构、磁性及在催化苄胺偶联反应中的应用  

Synthesis,Structure,Magnetism of a Thorium-Iron Oxo Cluster and Its Application in Catalyzing the Coupling Reaction of Benzylamine

作　　者：王春晖 张洋[1] 韩哲 高原[1] 何普涌 范超越 邱杰 WANG Chunhui;ZHANG Yang;HAN Zhe;GAO Yuan;HE Puyong;FAN Chaoyue;QIU Jie*(School of Energy and Power Engineering,Xi’an Jiaotong University,Xi’an 710049,China)

机构地区：[1]西安交通大学能源与动力工程学院,西安710049

出　　处：《高等学校化学学报》2025年第3期1-10,共10页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:22076152,22276147,21806127)资助。

摘　　要：采用溶剂热法合成了一种新型带负电的钍-铁金属氧簇[Th_(2)Fe_(10)O_(4)(C_6H_(5)PO_(3))_(12)(CH_(3)O)_(8)Cl_(4)]^(6-)(Th_(2)Fe_(10)),并表征了其晶体结构、化学组成、磁性质和催化性能.单晶X射线衍射数据显示,Th_(2)Fe_(10)为一种新型十二核Th-Fe金属氧簇,Th(Ⅳ)和Fe(Ⅲ)离子的协同水解、醇解和缩聚反应以及苯基膦酸根的钝化作用促进了该簇合物的形成.Th_(2)Fe_(10)不仅是第二例被报道的Th-Fe氧簇,也是为数不多的锕系-过渡金属氧簇之一.光性质和磁性质表征结果表明,Th_(2)Fe_(10)晶体具有显著的吸收可见光的特性,且Fe(Ⅲ)离子间展现出强的反铁磁交换作用.催化反应结果表明,Th_(2)Fe_(10)具有优良的催化苄胺偶联反应的性能,实现了高达94%的转化率和96%的选择性,且经过多次循环使用后,仍保持良好的催化性能.活性物种清除实验表明,电子、空穴、^(1)O_(2)和·OH在催化过程中具有重要作用,并通过电化学测试和电子顺磁共振谱(EPR)进行了验证.基于以上实验结果推测了催化反应机理.A novel negatively charged thorium-iron oxo cluster,[Th_(2)Fe_(10)O_(4)(C_(6)H_(5)PO_(3))_(12)(CH_(3)O)_(8)Cl_(4)]^(6-)(Th_(2)Fe_(10)) was synthesized via the solvothermal method.Multiple techniques were employed to investigate its structure,chemical compositions,magnetic properties and catalytic performance.Single-crystal X-ray diffraction data revealed that the structure of Th_(2)Fe_(10) represents a novel dodecanuclear Th-Fe oxo cluster,which is formed due to the synergistic hydrolysis,alcoholysis and condensation reactions of Th(Ⅳ)and Fe(Ⅲ)ions,along with the passivation by phenylphosphonate groups.Th_(2)Fe_(10) is not only the second reported Th-Fe oxo cluster,but also one of the few actinide-transition metal oxo clusters.The crystals of Th_(2)Fe_(10) exhibit remarkable visible light absorption properties and strong antiferromagnetic exchange interactions between Fe(Ⅲ)ions.Moreover,Th_(2)Fe_(10) possesses excellent performance in catalyzing the benzylamine coupling reaction,achieving up to 94%conversion and 96%selectivity,while maintaining good catalytic performance after multiple cycles.Scavenging experiments of reactive species demonstrated that electrons,holes,^(1)O_(2) and·OH play significant roles in the catalytic process,which was further verified through electrochemical measurements and electron paramagnetic resonance(EPR) spectroscopy.The catalytic reaction mechanism was postulated based on these experimental results.

关 键 词：异金属氧簇 钍-铁氧簇 磁性 催化性能 苄胺偶联反应 

分 类 号：O614[理学—无机化学]