Synthesis Of Tripod Complexes And Their Application In Photocatalytic Reduction Of CO₂

The study of photocatalytic carbon dioxide reduction is one of the ways for mankind to use solar energy to catalyze the generation of valuable carbon-containing reducing substances,and one of the effective ways to realize artificial carbon cycle,which plays an important role in alleviating energy crisis and greenhouse effect.At present,the low activity,low stability and low selectivity of reduction products of photocatalyst hinder the efficient utilization of photocatalytic carbon dioxide.Therefore,the design of new photocatalyst with high activity and high stability is the key to effectively improve the performance of photocatalytic system.Based on the above problems,a new tripod ligand was designed and synthesized in this paper and made into cobalt-based catalyst for the study of photocatalytic Carbon dioxide.The experimental results are as follows:A tripod with the cavity structure was synthesized by molecular ligands cage,synthesis,and success will be copper???and cobalt???ions in the cavity of ligand,coordination by NMR,MS,X-ray single crystal diffraction for the structural characterization of related substances.The two complexes catalyzed by light carbon dioxide reduction research,the results show that the closed structure of the tripod copper???and cobalt???complexes against its photocatalytic performance boost.Connection on the activation of graphene oxide three?2 aminoethyl?amine with modification of graphene oxide GO-TREN,load cobalt???ions on the surface with a heterogeneous catalyst light GO-TREN-Co.It was characterized by XPS ion chromatography and used in photocatalytic carbon dioxide reduction at 0.1 mg/group.The results showed that under the conditions of 0.4?M[Ru?phen?₃]?PF₆?₂ as photosensitive agent,0.3 M TEOA as sacrifying agent and pure Me CN,the catalytic reaction produced 3.43?mol CO and 0.046?mol H₂ for 10 h,TON?CO?was 470,and the selectivity of CO was 98.7%.A new tripod ligand NTP was prepared by dehydration condensation reaction.Then NTP was used as the ligand to synthesize tripod complex NTP-CO.Its structure was characterized by NMR,MS,and it was used in photocatalytic CO₂reduction reaction.Through the screening of different sacrificial agent,solvent,such as conditions,choose suitable for optimal catalytic system,the experimental results show that under the concentration of 0.05?M,with 0.4 m M[Ru?phen?₃]?PF₆?₂as the photosensitizer,0.3 M TEOA as sacrificial agent,solvent for pure Me CN conditions,catalytic reaction 8 h,0.040?mol H₂ and 1.1?mol CO,TON?CO?for 4400,CO selectivity of 97.3%.