Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electro...Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electrocatalytic reaction kinetics at the cathode.The integration of light energy into Zn/Sn-air batteries is a promising strategy for enhancing their performance.However,the photothermal and photoelectric effects generate heat in the battery under prolonged solar irradiation,leading to air cathode instability.This paper presents the first design and synthesis of Ni_(2)-1,5-diamino-4,8-dihydroxyanthraquinone(Ni_(2)DDA),an electronically conductiveπ-d conjugated metal-organic framework(MOF).Ni_(2)DDA exhibits both photoelectric and photothermal effects,with an optical band gap of~1.14 eV.Under illumination,Ni_(2)DDA achieves excellent oxygen evolution reaction performance(with an overpotential of 245 mV vs.reversible hydrogen electrode at 10 mA cm^(−2))and photothermal stability.These properties result from the synergy between the photoelectric and photothermal effects of Ni_(2)DDA.Upon integration into Zn/Sn-air batteries,Ni_(2)DDA ensures excellent cycling stability under light and exhibits remarkable performance in high-temperature environments up to 80℃.This study experimentally confirms the stable operation of photo-assisted Zn/Sn-air batteries under high-temperature conditions for the first time and provides novel insights into the application of electronically conductive MOFs in photoelectrocatalysis and photothermal catalysis.展开更多
A thorough understanding of the growth behaviors of Zn anode at various temperatures is essential for improving the lifespan of Zn-based flow batteries(ZFBs).However,the impact of temperature on Zn deposition in ZFBs ...A thorough understanding of the growth behaviors of Zn anode at various temperatures is essential for improving the lifespan of Zn-based flow batteries(ZFBs).However,the impact of temperature on Zn deposition in ZFBs has not been thoroughly investigated.In this work,we find that at low temperatures(0–40°C)Zn deposit presents a dense and smooth morphology with minimal side reactions,such as hydrogen evolution and aqueous corrosion.Above 60°C,Zn begins to grow vertically on the substrate,forming larger particles and intensifying side reactions.These differences in Zn growth behaviors at varying temperatures are closely linked to changes in Zn nucleation,as observed through in situ atomic force microscopy.Consequently,elevated temperature in a ZFB promotes preferentially vertical deposition of Zn at the membrane/electrode interface,extending into the membrane.As a result,this significantly hinders ion transport across the membrane and substantially increases the risk of short-circuiting.This process is the primary factor contributing to the reduced lifespan of ZFBs at high temperatures.展开更多
高炉煤气中硫化氢(H_(2)S)的脱除对实现钢铁行业超低排放具有重要意义。高炉煤气经余压透平发电装置(Blast Furnace Top Gas Recovery Turbine Unit,TRT)后,温度在50~80℃之间,宜选用低温下活性较高的针铁矿(α-FeOOH)作为高炉煤气水解...高炉煤气中硫化氢(H_(2)S)的脱除对实现钢铁行业超低排放具有重要意义。高炉煤气经余压透平发电装置(Blast Furnace Top Gas Recovery Turbine Unit,TRT)后,温度在50~80℃之间,宜选用低温下活性较高的针铁矿(α-FeOOH)作为高炉煤气水解后H_(2)S的吸附剂。采用共沉淀结晶法将不同摩尔比(1%、5%、11%)的Zn^(2+)掺杂到α-FeOOH中,在模拟的高炉煤气气氛中,利用固定床-气相色谱联用平台测试其对H_(2)S的吸附容量,Zn/FeOOH硫容提升至292.2 mg/g,提高了137%。采用BET、EPR、XPS等分析手段对吸附剂的理化性质进行表征,分析结果表明,Zn/FeOOH样品的比表面积提升近60%。比表面积的增加意味着更多的反应界面可用于H_(2)S的吸附和转化,更多的吸附位点是提高硫容的关键因素之一。此外,孔容积提升约116%,孔容积的增加可以缓解反应产物带来的孔道堵塞效应。在g=2.002的位置,Zn/FeOOH系列样品均出现了氧空位的特征峰,Zn/FeOOH-11样品表现出最高的氧空位信号强度,表明掺杂Zn后材料中的氧空位显著增加。当Zn^(2+)被引入α-FeOOH晶格时,由于Zn^(2+)和Fe3+的离子半径和电荷不完全匹配,其替代Fe3+会在晶格中引入局部应力和畸变,有助于氧原子从晶格中逸出,形成氧空位。氧空位能为H_(2)S的吸附和活化提供活性位点,增强材料的催化活性。Zn掺杂α-FeOOH中单羟基比例增加到36%。单羟基是提高硫容的关键,作为活性较高的基团能够与H_(2)S形成氢键,从而增强材料表面的吸附。通过原位红外光谱分析,表明Zn不仅作为催化剂的一部分,还直接参与H_(2)S的反应形成ZnS,Zn掺杂不仅改善了α-FeOOH的催化性能,还影响了硫产物的种类。结构和表面性能的改变,显著提升了Zn/FeOOH材料对H_(2)S的吸附和转化能力,为吸附剂硫容提高及高炉煤气净化技术应用提供了参考。展开更多
Deficiency or restriction of Zn absorption in soils is one of the most common micronutrients deficient in cereal plants. To investigate critical micronutrient interaction in zinc deficiency and zinc sufficient in soil...Deficiency or restriction of Zn absorption in soils is one of the most common micronutrients deficient in cereal plants. To investigate critical micronutrient interaction in zinc deficiency and zinc sufficient in soil, a factorial experiment based on completely randomized design (CRD) with three replications was conducted in 2023. Six wheat cultivars with different Zn efficiency were used. The cultivars were grown under Zn deficiency and adequate conditions. Results showed that in Zn deficiency conditions, with increasing Zn concentration in the roots, Fe concentrations were increased too, while the Cu and Mn concentrations decreased. In the same condition and with increasing Zn concentration in shoots, the concentrations of Fe and Mn decreased, while Cu were increased. However, by increasing Zn concentration, Fe, Cu, and Mn concentrations were increased in Zn deficiency condition in grains, as well as Zn sufficient conditions. RST (root to shoot micronutrient translocation) comparison of cultivars showed that in lack of Zn, the ability of translocation of Zn, Fe, and Mn in Zn-inefficient cultivar from root to shoot was higher than inefficient cultivar. In the same conditions, the capability of Zn-inefficient cultivar in Cu translocation from root to shoot was lower than other cultivars. In general, it seems that in Zn deficiency conditions, there are antagonistic effects among Zn, Cu and Mn and synergistic effects between Zn and Fe in the root. Also, in Zn sufficient conditions, there were synergistic effects among all studies micronutrients which include Zn, Fe, Cu, and Mn.展开更多
基金supported by the National Natural Science Foundation of China(No.62464010)Spring City Plan-Special Program for Young Talents(K202005007)+2 种基金Yunnan Talents Support Plan for Young Talents(XDYC-QNRC-2022-0482)Yunnan Local Colleges Applied Basic Research Projects(202101BA070001-138)Frontier Research Team of Kunming University 2023.
文摘Rechargeable Zn/Sn-air batteries have received considerable attention as promising energy storage devices.However,the electrochemical performance of these batteries is significantly constrained by the sluggish electrocatalytic reaction kinetics at the cathode.The integration of light energy into Zn/Sn-air batteries is a promising strategy for enhancing their performance.However,the photothermal and photoelectric effects generate heat in the battery under prolonged solar irradiation,leading to air cathode instability.This paper presents the first design and synthesis of Ni_(2)-1,5-diamino-4,8-dihydroxyanthraquinone(Ni_(2)DDA),an electronically conductiveπ-d conjugated metal-organic framework(MOF).Ni_(2)DDA exhibits both photoelectric and photothermal effects,with an optical band gap of~1.14 eV.Under illumination,Ni_(2)DDA achieves excellent oxygen evolution reaction performance(with an overpotential of 245 mV vs.reversible hydrogen electrode at 10 mA cm^(−2))and photothermal stability.These properties result from the synergy between the photoelectric and photothermal effects of Ni_(2)DDA.Upon integration into Zn/Sn-air batteries,Ni_(2)DDA ensures excellent cycling stability under light and exhibits remarkable performance in high-temperature environments up to 80℃.This study experimentally confirms the stable operation of photo-assisted Zn/Sn-air batteries under high-temperature conditions for the first time and provides novel insights into the application of electronically conductive MOFs in photoelectrocatalysis and photothermal catalysis.
基金financially supported by National Key R&D Program of China (2022YFA1504500)National Natural Science Foundation of China (22372158, 21825203, 22332006, 22288201, 22209179, 22478379 and 22379142)Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0600300)
文摘A thorough understanding of the growth behaviors of Zn anode at various temperatures is essential for improving the lifespan of Zn-based flow batteries(ZFBs).However,the impact of temperature on Zn deposition in ZFBs has not been thoroughly investigated.In this work,we find that at low temperatures(0–40°C)Zn deposit presents a dense and smooth morphology with minimal side reactions,such as hydrogen evolution and aqueous corrosion.Above 60°C,Zn begins to grow vertically on the substrate,forming larger particles and intensifying side reactions.These differences in Zn growth behaviors at varying temperatures are closely linked to changes in Zn nucleation,as observed through in situ atomic force microscopy.Consequently,elevated temperature in a ZFB promotes preferentially vertical deposition of Zn at the membrane/electrode interface,extending into the membrane.As a result,this significantly hinders ion transport across the membrane and substantially increases the risk of short-circuiting.This process is the primary factor contributing to the reduced lifespan of ZFBs at high temperatures.
文摘高炉煤气中硫化氢(H_(2)S)的脱除对实现钢铁行业超低排放具有重要意义。高炉煤气经余压透平发电装置(Blast Furnace Top Gas Recovery Turbine Unit,TRT)后,温度在50~80℃之间,宜选用低温下活性较高的针铁矿(α-FeOOH)作为高炉煤气水解后H_(2)S的吸附剂。采用共沉淀结晶法将不同摩尔比(1%、5%、11%)的Zn^(2+)掺杂到α-FeOOH中,在模拟的高炉煤气气氛中,利用固定床-气相色谱联用平台测试其对H_(2)S的吸附容量,Zn/FeOOH硫容提升至292.2 mg/g,提高了137%。采用BET、EPR、XPS等分析手段对吸附剂的理化性质进行表征,分析结果表明,Zn/FeOOH样品的比表面积提升近60%。比表面积的增加意味着更多的反应界面可用于H_(2)S的吸附和转化,更多的吸附位点是提高硫容的关键因素之一。此外,孔容积提升约116%,孔容积的增加可以缓解反应产物带来的孔道堵塞效应。在g=2.002的位置,Zn/FeOOH系列样品均出现了氧空位的特征峰,Zn/FeOOH-11样品表现出最高的氧空位信号强度,表明掺杂Zn后材料中的氧空位显著增加。当Zn^(2+)被引入α-FeOOH晶格时,由于Zn^(2+)和Fe3+的离子半径和电荷不完全匹配,其替代Fe3+会在晶格中引入局部应力和畸变,有助于氧原子从晶格中逸出,形成氧空位。氧空位能为H_(2)S的吸附和活化提供活性位点,增强材料的催化活性。Zn掺杂α-FeOOH中单羟基比例增加到36%。单羟基是提高硫容的关键,作为活性较高的基团能够与H_(2)S形成氢键,从而增强材料表面的吸附。通过原位红外光谱分析,表明Zn不仅作为催化剂的一部分,还直接参与H_(2)S的反应形成ZnS,Zn掺杂不仅改善了α-FeOOH的催化性能,还影响了硫产物的种类。结构和表面性能的改变,显著提升了Zn/FeOOH材料对H_(2)S的吸附和转化能力,为吸附剂硫容提高及高炉煤气净化技术应用提供了参考。
文摘Deficiency or restriction of Zn absorption in soils is one of the most common micronutrients deficient in cereal plants. To investigate critical micronutrient interaction in zinc deficiency and zinc sufficient in soil, a factorial experiment based on completely randomized design (CRD) with three replications was conducted in 2023. Six wheat cultivars with different Zn efficiency were used. The cultivars were grown under Zn deficiency and adequate conditions. Results showed that in Zn deficiency conditions, with increasing Zn concentration in the roots, Fe concentrations were increased too, while the Cu and Mn concentrations decreased. In the same condition and with increasing Zn concentration in shoots, the concentrations of Fe and Mn decreased, while Cu were increased. However, by increasing Zn concentration, Fe, Cu, and Mn concentrations were increased in Zn deficiency condition in grains, as well as Zn sufficient conditions. RST (root to shoot micronutrient translocation) comparison of cultivars showed that in lack of Zn, the ability of translocation of Zn, Fe, and Mn in Zn-inefficient cultivar from root to shoot was higher than inefficient cultivar. In the same conditions, the capability of Zn-inefficient cultivar in Cu translocation from root to shoot was lower than other cultivars. In general, it seems that in Zn deficiency conditions, there are antagonistic effects among Zn, Cu and Mn and synergistic effects between Zn and Fe in the root. Also, in Zn sufficient conditions, there were synergistic effects among all studies micronutrients which include Zn, Fe, Cu, and Mn.
