氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过...氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。展开更多
Metastable nanostructured electrocatalyst with a completely different surface environment compared to conventional phase-based electrocatalyst often shows distinctive catalytic property.Although Ru-based electrocataly...Metastable nanostructured electrocatalyst with a completely different surface environment compared to conventional phase-based electrocatalyst often shows distinctive catalytic property.Although Ru-based electrocatalysts have been widely investigated toward hydrogen oxidation reaction(HOR)under alkaline electrolytes,these studies are mostly limited to conventional hexagonal-close-packed(hcp)phase,mainly arising from the lack of sufficient synthesis strategies.In this study,we report the precise synthesis of metastable binary RuW alloy with face-centered-cubic(fcc)phase.We find that the introduction of W can serve as fcc phase seeds and reduce the formation energy of metastable fcc-RuW alloy.Impressively,fcc-RuW exhibits remarkable alkaline HOR performance and stability with the activity of 0.67 mA cm_(Ru)^(-2)which is almost five and three times higher than that of hcp-Ru and commercial Pt/C,respectively,which is attributed to the optimized binding strength of adsorbed hydroxide intermediate derived from tailored electronic structure through W doping and phase engineering.Moreover,this strategy can also be applied to synthesize other metastable fcc-RuCr and fcc-RuMo alloys with enhanced HOR performances.展开更多
A fourth generation single crystal(SC)nickel based cast superalloy DD15 with 1%Ru,3%Ru,5%Ru was prepared using vacuum induction single crystal furnace in order to optimize the properties and cost of DD15 alloy.The exp...A fourth generation single crystal(SC)nickel based cast superalloy DD15 with 1%Ru,3%Ru,5%Ru was prepared using vacuum induction single crystal furnace in order to optimize the properties and cost of DD15 alloy.The exposure experiment of three alloys was conducted at 1100℃for 1000 h.The stress rupture properties tests were performed at 1100℃temperature and 137 MPa pressure.The composition optimization of Ru element in DD15 alloy had been studied.It was found that the alloys with different Ru contents all consist of cuboidalγ′phase embedded coherent inγphase.Theγ′phase of the alloy all has a size of about 300-500 nm and a volume content of more than sixty percent.The dimension ofγ′precipitates is reduced and uniform with increase of Ru content.Ru element can reduce the distribution ratio of high melting point element,so the microstructural stability is enhanced with Ru content increasing.No topologically close-packed(TCP)phase precipitated in the 5%Ru alloy even after 1000 h exposure.The stress rupture life of the alloy is significantly improved as Ru content rising.The raft breadth decreases slightly as Ru content increases.The specimen with 1%Ru and 3%Ru exhibits the presence of TCP phases and without TCP phases precipitated in fracture specimen with 5%Ru.The density and integrity ofγ/γ′interfacial dislocation network increase as Ru content of the alloy rises.展开更多
对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2...对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。展开更多
文摘氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。
基金the support from the National Natural Science Foundation of China(22272121,21972107)the National Key Research and Development program of China(2021YFB4001200)。
文摘Metastable nanostructured electrocatalyst with a completely different surface environment compared to conventional phase-based electrocatalyst often shows distinctive catalytic property.Although Ru-based electrocatalysts have been widely investigated toward hydrogen oxidation reaction(HOR)under alkaline electrolytes,these studies are mostly limited to conventional hexagonal-close-packed(hcp)phase,mainly arising from the lack of sufficient synthesis strategies.In this study,we report the precise synthesis of metastable binary RuW alloy with face-centered-cubic(fcc)phase.We find that the introduction of W can serve as fcc phase seeds and reduce the formation energy of metastable fcc-RuW alloy.Impressively,fcc-RuW exhibits remarkable alkaline HOR performance and stability with the activity of 0.67 mA cm_(Ru)^(-2)which is almost five and three times higher than that of hcp-Ru and commercial Pt/C,respectively,which is attributed to the optimized binding strength of adsorbed hydroxide intermediate derived from tailored electronic structure through W doping and phase engineering.Moreover,this strategy can also be applied to synthesize other metastable fcc-RuCr and fcc-RuMo alloys with enhanced HOR performances.
基金Sponsored by the National Science and Technology Major Project(Grant No.2017-VI-0002-0071)。
文摘A fourth generation single crystal(SC)nickel based cast superalloy DD15 with 1%Ru,3%Ru,5%Ru was prepared using vacuum induction single crystal furnace in order to optimize the properties and cost of DD15 alloy.The exposure experiment of three alloys was conducted at 1100℃for 1000 h.The stress rupture properties tests were performed at 1100℃temperature and 137 MPa pressure.The composition optimization of Ru element in DD15 alloy had been studied.It was found that the alloys with different Ru contents all consist of cuboidalγ′phase embedded coherent inγphase.Theγ′phase of the alloy all has a size of about 300-500 nm and a volume content of more than sixty percent.The dimension ofγ′precipitates is reduced and uniform with increase of Ru content.Ru element can reduce the distribution ratio of high melting point element,so the microstructural stability is enhanced with Ru content increasing.No topologically close-packed(TCP)phase precipitated in the 5%Ru alloy even after 1000 h exposure.The stress rupture life of the alloy is significantly improved as Ru content rising.The raft breadth decreases slightly as Ru content increases.The specimen with 1%Ru and 3%Ru exhibits the presence of TCP phases and without TCP phases precipitated in fracture specimen with 5%Ru.The density and integrity ofγ/γ′interfacial dislocation network increase as Ru content of the alloy rises.
文摘对Ru59063的合成进行了改进。首先,4-氨基-2-(三氟甲基)苯甲腈(Ⅲ)与硫光气反应,制备了4-异硫氰基-2-(三氟甲基)苯腈(Ⅳ);然后,中间体Ⅳ与2-氨基异丁酸甲酯盐酸盐进行[3+2]环加成反应,合成了4-(2-硫代-4,4-二甲基-5-氧代咪唑烷-1-基)-2-三氟甲基苯腈(Ⅶ);化合物Ⅶ再与叔丁基-(4-氯丁氧基)-二甲基硅烷通过乌尔曼C—N偶联反应,得到了4-{3-[4-(叔丁基二甲基硅基)-羟基丁基]-4,4-二甲基-5-氧代-2-硫代咪唑烷-1-基}-2-(三氟甲基)苯甲腈(Ⅷ);最后,中间体Ⅷ进行羟基脱保护得到Ru59063,4步反应总收率为61.6%,HPLC纯度为98.2%。与传统方法相比,该法收率提高了4.7倍,并且未使用氰化物,可以更方便、更安全地制备了Ru59063。对2 kg 4-氨基-2-(三氟甲基)苯甲腈进行了放大实验,总收率可达到60.7%。
