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
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.
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%。
