| Based on the traditional synthetic method,this project developed a scheme to design and synthesize metal complex templated borate with novel hybrid structures and physical properties by introducing 1-methylimidazole and N,N-dimethylethylenediamine as ligands.These compounds have been characterized by elemental analysis,IR and PXRD.And we will explore their ORR activity.In the synthesis of[Ni(1-MI)6]·[B(OH)3]4·SO4(1),we obtained crystals by using barium hydroxide to remove part of the sulfate ions in the system.The crystallographic data are as follows.Tetragonal,P4/n,a=20.8015(5),b=20.8015(5),c=9.7315(2),a=90°,b=90°,g=90°,Z=2.It exhibited wide band gap(4.4 e V),and ORR activities with a half-wave potential of 0.78 V for 1 by heat treatment for 450?.In the synthesis of[Ni(H2O)3(1-MI)3]·[B5O6(OH)4]2(2),we obtained crystals by using barium hydroxide to remove all the sulfate ions in the system.The crystallographic data are as follows.Monoclinic,P21/n,a=17.8428(3),b=11.2042(2),c=33.9565(7),a=90°,b=104.0460(10)°,g=90°,Z=4.It exhibited wide band gap(4.5 e V),and ORR activities with a half-wave potential of 0.76 V for 2 by heat treatment for 450?.In the synthesis of[(C4H7N2)2]·Co[B6O7(OH)6]2·2H2O(3),we obtained crystals by replacing the metal element with cobalt,and the ORR activity was significantly improved.The crystallographic data are as follows.Orthorhombic,Fdd2,a=16.8695(3),b=22.3910(5),c=14.9744(3),a=90°,b=90°,g=90°,Z=4.It exhibited wide band gap(5.12 e V),and ORR activities with a half-wave potential of 0.82 V for 3 by heat treatment for 450?.In the synthesis of[Co(1-MI)2]·B5O7(OH)3(4)and[Zn(1-MI)2]·B5O7(OH)3(5),we obtained crystals by employing the solvothermal method as the main synthesis method.The crystallographic data of 4 are as follows.Triclinic,P-1,a=8.9576(10),b=9.4001(11),c=11.9155(12),a=91.927(4)°,b=102.862(3)°,g=115.726(3)°,Z=2.he crystallographic data of 5 are as follows.Triclinic,P-1,a=8.9502(10),b=9.4074(12),c=11.9069(16),a=91.927(5)°,b=102.835(4)°,g=115.689(4)°,Z=2.It exhibited wide band gap(5.14 e V),and ORR activities with a half-wave potential of 0.83 V for 4 by heat treatment for 600?.And it exhibited wide band gap(5.10 e V),and ORR activities with a half-wave potential of0.73 V for 5 by heat treatment for 450?.In the synthesis of[Ni(C4H12N2)]·[B6O7(OH)6]·3.5H2O(6),by changing the organic ligands for comparison,we obtained crystals by introducing N,N-dimethylethylenediamine as a ligand to participate in the reaction.The crystallographic data are as follows.Triclinic,P-1,a=9.3437(3),b=15.1083(6),c=18.2743(9),?=89.0930(10)°,?=85.6290(10)°,?=84.979(2)°,Z=4.It exhibited wide band gap(4.4 eV),and ORR activities with a half-wave potential of 0.78 V for 6 by heat treatment for 450?.In the synthesis of[Ni(H2O)2(C4H12N2)2]·[B5O6(OH)4]2·2H2O(7),we obtained crystals by employing the solvothermal method as the main synthesis method.The crystallographic data are as follows.Triclinic,P-1,a=8.6782(4)(?),b=9.7396(5)(?),c=10.2055(5)(?),?=107.007(2)°,?=102.712(2)°,?=94.934(2)°,Z=2.It exhibited wide band gap(4.24 e V),and ORR activities with a half-wave potential of 0.76 V for 7 by heat treatment for 450?. |
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