Zhang Peng-Yun, Lian Chen, Wang Zhen-Wen, Chen Juan, Lv Hongjin, Yang Guo-Yu
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China.
Dalton Trans. 2024 Aug 13;53(32):13409-13415. doi: 10.1039/d4dt00928b.
Two Ni-added poly(polyoxometalate)s built of Keggin-type {NiPW} and Anderson-type NiWO units WO/SbO bridges and Ni-O-W linkages, NaH[Ni(enMe)][(SbO)(NiWO)-{NiO(OH)(enMe)(HO)(WO)(B-α-PWO)}]·39HO (1) and H[Ni(en)(HO)][Ni(en)(HO)][Ni-(enMe)(HO)][(SbO)(NiWO){NiO(OH)(en)(enMe)(HO)(WO)}-{NiO(OH)(en)(HO)(WO)}(B-α-PWO)]·45HO (2), have been hydrothermally synthesized and characterized, in which the {Ni(WO)(PW)} subunit was obtained by the synergistic directing effect of 2 lacunary PWO (PW) fragments and further linked by a central Anderson-type (SbO)(NiWO) bridge. Both compounds represent the first example of Ni-added polyoxometalates (POMs) simultaneously based on Keggin-type and Anderson-type POM components. Photocatalytic studies revealed that 2 can work as an efficient heterogeneous catalyst towards a light-driven H evolution reaction, achieving a hydrogen evolution rate of as high as 19 214 μmol g h (TON = 1500), which is superior to most of the reported POM-based heterogeneous catalysts.
通过水热法合成并表征了两种由Keggin型{NiPW}和Anderson型NiWO单元、WO/SbO桥及Ni-O-W键连接而成的含镍多金属氧酸盐，NaH[Ni(enMe)][(SbO)(NiWO)-{NiO(OH)(enMe)(HO)(WO)(B-α-PWO)}]·39HO (1) 和H[Ni(en)(HO)][Ni(en)(HO)][Ni-(enMe)(HO)][(SbO)(NiWO){NiO(OH)(en)(enMe)(HO)(WO)}-{NiO(OH)(en)(HO)(WO)}(B-α-PWO)]·45HO (2)，其中{Ni(WO)(PW)}亚基是通过两个缺位PWO (PW)片段的协同导向作用得到的，并通过中心Anderson型(SbO)(NiWO)桥进一步连接。这两种化合物均代表了同时基于Keggin型和Anderson型多金属氧酸盐组分的含镍多金属氧酸盐（POMs）的首例。光催化研究表明，2可作为光驱动析氢反应的高效非均相催化剂，析氢速率高达19 214 μmol g h（TON = 1500），优于大多数已报道的基于POM的非均相催化剂。
