Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperature...Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization.This article reports two series of asymmetrically alkyl-grafted azobenzene(Azo-g),with and without a methyl group,that have an optically triggered phase change.Three exothermic modes were designed to utilize crystallization enthalpy(△H_(c))and photothermal(isomerization)energy(△H_(p))at different temperatures determined by the crystallization.Azo-g has high heat output(275-303 J g^(-1))by synchronously releasing△H_(c)and△H_(p)over a wide temperature range(-79℃to 25℃).We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6℃at a temperature of-8℃.The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.展开更多
Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_...Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_(2)}{[Ni_(6)Cl(μ-OH)_(3)(H_(2)O)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))][Ni_(6)(μ-OH)_(3)(H_(2)O)_(2)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))]}Cl·27H_(2)O,(1,Dach=1,2-diaminocyclohexane)was synthesized.Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene(AOB)in water.The apparently different results from that with the matrix{PW_(9)O_(34)}({PW9})suggest the successful regulation of the catalytic property of{PW9}by the introduction of the{Ni6}cluster into the skeleton.The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites,which are respectively responsible for the oxidation and condensation steps in the production of AOB.The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites,respectively.展开更多
基金financially supported by National Key R&D Program of China(No.2022YFB3805702)the State Key Program of National Natural Science Foundation of China(No.52130303)
文摘Photoisomerization-induced phase change are important for co-harvesting the latent heat and isomerization energy of azobenzene molecules.Chemically optimizing heat output and energy delivery at alternating temperatures are challenging because of the differences in crystallizability and isomerization.This article reports two series of asymmetrically alkyl-grafted azobenzene(Azo-g),with and without a methyl group,that have an optically triggered phase change.Three exothermic modes were designed to utilize crystallization enthalpy(△H_(c))and photothermal(isomerization)energy(△H_(p))at different temperatures determined by the crystallization.Azo-g has high heat output(275-303 J g^(-1))by synchronously releasing△H_(c)and△H_(p)over a wide temperature range(-79℃to 25℃).We fabricated a new distributed energy utilization and delivery system to realize a temperature increase of 6.6℃at a temperature of-8℃.The findings offer insight into selective utilization of latent heat and isomerization energy by molecular optimization of crystallization and isomerization processes.
基金supported by the National Natural Science Foundation of China(Nos.21773247,22275185,21521061,21875252)the Natural Science Foundation of Fujian Province(No.2006L2005).
文摘Partial substitution of polyoxometalate(POM)is an efficient route to modulate the catalytic property of maternal POM.In this work,a new Keggin type POM involving{Ni 6}cluster,{[Ni(H_(2)O)_(2)(Dach)_(2)][Ni(Dach)_(2)]_(2)}{[Ni_(6)Cl(μ-OH)_(3)(H_(2)O)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))][Ni_(6)(μ-OH)_(3)(H_(2)O)_(2)(Dach)_(3)(WO_(4))(PW9 O_(3)_(4))]}Cl·27H_(2)O,(1,Dach=1,2-diaminocyclohexane)was synthesized.Compounds 1 shows excellent catalytic performance in the selective oxidation of aniline to azoxybenzene(AOB)in water.The apparently different results from that with the matrix{PW_(9)O_(34)}({PW9})suggest the successful regulation of the catalytic property of{PW9}by the introduction of the{Ni6}cluster into the skeleton.The experimental results indicate that the highlighted performance of 1 is contributed by the synergy of W and Ni sites,which are respectively responsible for the oxidation and condensation steps in the production of AOB.The good selectivity to AOB is essentially attributed to the effective modulation of the reaction rates of oxidation and condensation steps by W and Ni sites,respectively.
