The high-pressure structural,vibrational and electrical properties for realgar were investigated by in-situ Raman scattering and electrical conductivity experiments combined with first-principle calculations up to~30....The high-pressure structural,vibrational and electrical properties for realgar were investigated by in-situ Raman scattering and electrical conductivity experiments combined with first-principle calculations up to~30.8 GPa.It was verified that realgar underwent an isostructural phase transition at~6.3 GPa and a metallization at a higher pressure of~23.5 GPa.The isostructural phase transition was well evidenced by the obvious variations of Raman peaks,electrical conductivity,crystal parameters and the As–S bond length.The phase transition of metallization was in closely associated with the closure of bandgap rather than caused by the structural phase transition.And furthermore,the metallic realgar exhibited a relatively low compressibility with the unit cell volume V_(0)=718.1.4Å^(3)and bulk modulus B_(0)=36.1 GPa.展开更多
The launch of International Thermonuclear Experimental Reactor project paves the way to wide adoption of DT fusion energy as future energy source.Efficient fuel cycle to minimize strategic tritium inventory proves cru...The launch of International Thermonuclear Experimental Reactor project paves the way to wide adoption of DT fusion energy as future energy source.Efficient fuel cycle to minimize strategic tritium inventory proves crucial for commercially viable fusion technologies.ZrCo alloy is considered as a promising candidate for fast isotope handling.However,cycling degradation caused by hydrogen-induced disproportionation results in severe tritium trapping,thus impeding its practical application.Herein,an isostructural transition is successfully constructed with low hysterisis,ameliorated plateau flatness of pressure-composition isotherms and improved high-temperature durability for hydrogen trapping minimization.Specifically,the optimal Zr_(0.7)Hf_(0.15)Nb_(0.15)Co_(0.6)Cu_(0.15)Ni_(0.25) alloy adopts Hf-Nb and Cu-Ni as Zr and Co side doping elements,exhibiting substantial thermodynamic destabilization with nearly 90℃ reduction of delivery temperature,and significant kinetic promotion with a threefold lower energy barrier.More importantly,both hydrogen utilization and cycling retention of optimal alloy are increased by about twenty times compared with pristine alloy after 100 cycles at 500℃.Minimized disproportionation driving force from both isostructural transition and suppressed 8e hydrogen occupation realizes full potential of optimal alloy.This work demonstrates the effectiveness of combining isostructural transformation and high-temperature durability improvement to enhance the hydrogen utilization of ZrCo-based alloys and other hydrogen storage materials.展开更多
基金the strategic priority Research Program(B)of the Chinese Academy of Sciences(Grant No.18010401)Key Research Program of Frontier Sciences of CAS(Grant No.QYZDB-SSW-DQC009)+3 种基金Hundred Talents Program of CAS,NSF of China(Grant Nos.41774099 and 41772042)Youth Innovation Promotion Association of CAS(Grant No.2019390)Special Fund of the West Light Foundation of CASthe Supercomputer Center of Fujian Institute of Research on the Structure of Matter(FJIRSM)is acknowledged.
文摘The high-pressure structural,vibrational and electrical properties for realgar were investigated by in-situ Raman scattering and electrical conductivity experiments combined with first-principle calculations up to~30.8 GPa.It was verified that realgar underwent an isostructural phase transition at~6.3 GPa and a metallization at a higher pressure of~23.5 GPa.The isostructural phase transition was well evidenced by the obvious variations of Raman peaks,electrical conductivity,crystal parameters and the As–S bond length.The phase transition of metallization was in closely associated with the closure of bandgap rather than caused by the structural phase transition.And furthermore,the metallic realgar exhibited a relatively low compressibility with the unit cell volume V_(0)=718.1.4Å^(3)and bulk modulus B_(0)=36.1 GPa.
基金supports from the National Key Research and Development Program of China(2022YFE03170002)the National Natural Science Foundation of China(52071286 and U2030208).
文摘The launch of International Thermonuclear Experimental Reactor project paves the way to wide adoption of DT fusion energy as future energy source.Efficient fuel cycle to minimize strategic tritium inventory proves crucial for commercially viable fusion technologies.ZrCo alloy is considered as a promising candidate for fast isotope handling.However,cycling degradation caused by hydrogen-induced disproportionation results in severe tritium trapping,thus impeding its practical application.Herein,an isostructural transition is successfully constructed with low hysterisis,ameliorated plateau flatness of pressure-composition isotherms and improved high-temperature durability for hydrogen trapping minimization.Specifically,the optimal Zr_(0.7)Hf_(0.15)Nb_(0.15)Co_(0.6)Cu_(0.15)Ni_(0.25) alloy adopts Hf-Nb and Cu-Ni as Zr and Co side doping elements,exhibiting substantial thermodynamic destabilization with nearly 90℃ reduction of delivery temperature,and significant kinetic promotion with a threefold lower energy barrier.More importantly,both hydrogen utilization and cycling retention of optimal alloy are increased by about twenty times compared with pristine alloy after 100 cycles at 500℃.Minimized disproportionation driving force from both isostructural transition and suppressed 8e hydrogen occupation realizes full potential of optimal alloy.This work demonstrates the effectiveness of combining isostructural transformation and high-temperature durability improvement to enhance the hydrogen utilization of ZrCo-based alloys and other hydrogen storage materials.
