Thermocells are attracting growing interest as a promising thermoelectric technology for low-grade heat harvesting.However,the scarcity of high-performance redox couples featuring intrinsically high thermopower(Se)and...Thermocells are attracting growing interest as a promising thermoelectric technology for low-grade heat harvesting.However,the scarcity of high-performance redox couples featuring intrinsically high thermopower(Se)and fast redox kinetics hinders the rapid development of thermocells.Identifying potential intrinsically high-performance redox couples remains a significant challenge.This work introduces a novel n-type copper(I/II)chloride(CuCl/CuCl2)redox couple with intrinsically high performance.Through tailored electrolyte design,long-term stability was significantly improved by reducing proton concentration to suppress cuprous ion photo-oxidation,while ammonium chloride solvation enhanced cuprous ion solubility.The resulting system achieves a Se value closely aligned with theoretical predictions and exhibits rapid redox kinetics.Consequently,the optimized CuCl/CuCl_(2) intrinsic system demonstrated a high S_(e) of 1.52 mV K^(−1) and a record-high normalized power density Pmax(ΔT)^(−2) of 0.399 mW m^(−2) K^(−2),surpassing previously reported intrinsic n-type thermocells and rivaling the performance of p-type pristine 0.4 M ferri/ferrocyanide systems.A prototype module comprising 30 p-n units successfully powered a line of light-emitting diodes or a thermohygrometer.This work introduces a valuable redox couple for further advancing high-performance thermocells and demonstrates a viable strategy for developing novel redox systems.展开更多
Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-d...Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-dichlorophenylacetic acid （2,4-DCPA）, 4-chlorophenylacetic acid （4-DCPA）, 4,4＂-dipyridyl （4,4＂-bipy）, 1,3-bis（4-pyridyl）propane（bpp） and AgNO3. Compound 1 crystallizes in monoclinic, space group P21/c with a = 10.035（2）, b = 17.796（3）, c = 16.448（2） A, fl = 104.086（2）°, V= 2705.9（2） A3, Dc = 1.893 g/cm-3, C28H23C12NsO6Ag2, Mr = 812.15, F（000） = 1608,μ（MoKot） = 1.615 mm-1, Z = 4, R = 0.0310, wR = 0.0832 for 4357 observed reflections （I 〉 20（/））, and R = 0.0362, wR = 0.0873 for all data. Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.840（2）, b = 24.971（5）, c = 9.3301（2）°, fl = 117.504（2）°, V= 2033.5（7） A3, Dc = 1.666 g/cm3, C2tH19C12N202Ag, Mr = 510.15, F（000） = 1024,/I（MoKa） = 1.273 mml, Z= 4, R = 0.0315 and wR = 0.0680 for 2853 observed reflections （1 〉 20（/）） and R = 0.0454, wR = 0.0736 for all data. Compound 3 crystallizes in monoclinic, space group P21/n with a = 15.472（4）, b = 9.000（2）, c = 16.262（4） A, fl = 112.049（4）°, V = 2099.0（8） A3, Dc = 1.562 g/cm-3, C2H22C1N203Ag, Mr = 493.73, F（000） = 1000, μ（MoKa） = 1.111 mm-1, Z = 4, R = 0.0296, wR = 0.0821 for 3059 observed reflections （I 〉 2δ-（I））, and R = 0.0398, wR = 0.0986 for all data. The complexes were characterized by elemental analysis, FT-IR, thermogravimetrie analysis （TGA） and X-ray single-crystal structure analysis. Fluorescence properties of complex 3 and PXRD of 1 and 2 have been studied. As a result, in complex 1, the Ag（I） ion is surrounded by two nitrogen atoms from two bipy ligands to form an infinite chain, and adjacent Ag-bipy chains produce ＂＇rungs＂ of a ladder by silver ions contact. And in complexes 2 and 3, the two-dimensional ,β-sheet like layers are obtained by Ag……Ag interactions.展开更多
基金supported by research grants from Innovative Research Group Project of National Natural Science Foundation of China(52021004)the National Key Research and Development Program of China(2022YFB3803300)+1 种基金the National Natural Science Foundation of China(62474026,62205140,and 12204071)the China Postdoctoral Science Foundation(2022M710532).
文摘Thermocells are attracting growing interest as a promising thermoelectric technology for low-grade heat harvesting.However,the scarcity of high-performance redox couples featuring intrinsically high thermopower(Se)and fast redox kinetics hinders the rapid development of thermocells.Identifying potential intrinsically high-performance redox couples remains a significant challenge.This work introduces a novel n-type copper(I/II)chloride(CuCl/CuCl2)redox couple with intrinsically high performance.Through tailored electrolyte design,long-term stability was significantly improved by reducing proton concentration to suppress cuprous ion photo-oxidation,while ammonium chloride solvation enhanced cuprous ion solubility.The resulting system achieves a Se value closely aligned with theoretical predictions and exhibits rapid redox kinetics.Consequently,the optimized CuCl/CuCl_(2) intrinsic system demonstrated a high S_(e) of 1.52 mV K^(−1) and a record-high normalized power density Pmax(ΔT)^(−2) of 0.399 mW m^(−2) K^(−2),surpassing previously reported intrinsic n-type thermocells and rivaling the performance of p-type pristine 0.4 M ferri/ferrocyanide systems.A prototype module comprising 30 p-n units successfully powered a line of light-emitting diodes or a thermohygrometer.This work introduces a valuable redox couple for further advancing high-performance thermocells and demonstrates a viable strategy for developing novel redox systems.
基金supported by the Guangdong Science and Technology Department(No.S2012020011054 and 2011B090400415)the Zhanjiang Municipality(No.2011C3108001)projects
文摘Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-dichlorophenylacetic acid （2,4-DCPA）, 4-chlorophenylacetic acid （4-DCPA）, 4,4＂-dipyridyl （4,4＂-bipy）, 1,3-bis（4-pyridyl）propane（bpp） and AgNO3. Compound 1 crystallizes in monoclinic, space group P21/c with a = 10.035（2）, b = 17.796（3）, c = 16.448（2） A, fl = 104.086（2）°, V= 2705.9（2） A3, Dc = 1.893 g/cm-3, C28H23C12NsO6Ag2, Mr = 812.15, F（000） = 1608,μ（MoKot） = 1.615 mm-1, Z = 4, R = 0.0310, wR = 0.0832 for 4357 observed reflections （I 〉 20（/））, and R = 0.0362, wR = 0.0873 for all data. Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.840（2）, b = 24.971（5）, c = 9.3301（2）°, fl = 117.504（2）°, V= 2033.5（7） A3, Dc = 1.666 g/cm3, C2tH19C12N202Ag, Mr = 510.15, F（000） = 1024,/I（MoKa） = 1.273 mml, Z= 4, R = 0.0315 and wR = 0.0680 for 2853 observed reflections （1 〉 20（/）） and R = 0.0454, wR = 0.0736 for all data. Compound 3 crystallizes in monoclinic, space group P21/n with a = 15.472（4）, b = 9.000（2）, c = 16.262（4） A, fl = 112.049（4）°, V = 2099.0（8） A3, Dc = 1.562 g/cm-3, C2H22C1N203Ag, Mr = 493.73, F（000） = 1000, μ（MoKa） = 1.111 mm-1, Z = 4, R = 0.0296, wR = 0.0821 for 3059 observed reflections （I 〉 2δ-（I））, and R = 0.0398, wR = 0.0986 for all data. The complexes were characterized by elemental analysis, FT-IR, thermogravimetrie analysis （TGA） and X-ray single-crystal structure analysis. Fluorescence properties of complex 3 and PXRD of 1 and 2 have been studied. As a result, in complex 1, the Ag（I） ion is surrounded by two nitrogen atoms from two bipy ligands to form an infinite chain, and adjacent Ag-bipy chains produce ＂＇rungs＂ of a ladder by silver ions contact. And in complexes 2 and 3, the two-dimensional ,β-sheet like layers are obtained by Ag……Ag interactions.
