Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
以不同硅/铝摩尔比(简称硅/铝比)的HZSM-5分子筛作为研究对象,通过氨气吸附及程序升温脱附(NH_(3)-TPD)、烷烃吸附及程序升温脱附(Alkane-TPD)、29Si和27Al魔角转动固体核磁共振(29Si&27Al MAS SSNMR)、^(1)H和^(1)H双量子魔角转动...以不同硅/铝摩尔比(简称硅/铝比)的HZSM-5分子筛作为研究对象,通过氨气吸附及程序升温脱附(NH_(3)-TPD)、烷烃吸附及程序升温脱附(Alkane-TPD)、29Si和27Al魔角转动固体核磁共振(29Si&27Al MAS SSNMR)、^(1)H和^(1)H双量子魔角转动固体核磁共振(^(1)H&^(1)H DQ MAS SSNMR)等表征手段,研究了HZSM-5分子筛中Brønsted(B)酸中心的空间邻近性对烷烃分子吸附的特点,同时考察了空间邻近的B酸中心对烷烃单分子裂解选择性的影响。结果表明,随着HZSM-5分子筛硅/铝比的降低,分子筛中B酸中心空间邻近的几率增加,烷烃(丙烷、正丁烷和正戊烷)裂解的反应路径、选择性在邻近的B酸中心都与在孤立的酸中心上不同,显示出协同催化特点。其中,烷烃转化过程中裂解反应增加,脱氢反应减少,中间裂解产物相比于端基裂解产物具有更高的选择性。展开更多
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
文摘以不同硅/铝摩尔比(简称硅/铝比)的HZSM-5分子筛作为研究对象,通过氨气吸附及程序升温脱附(NH_(3)-TPD)、烷烃吸附及程序升温脱附(Alkane-TPD)、29Si和27Al魔角转动固体核磁共振(29Si&27Al MAS SSNMR)、^(1)H和^(1)H双量子魔角转动固体核磁共振(^(1)H&^(1)H DQ MAS SSNMR)等表征手段,研究了HZSM-5分子筛中Brønsted(B)酸中心的空间邻近性对烷烃分子吸附的特点,同时考察了空间邻近的B酸中心对烷烃单分子裂解选择性的影响。结果表明,随着HZSM-5分子筛硅/铝比的降低,分子筛中B酸中心空间邻近的几率增加,烷烃(丙烷、正丁烷和正戊烷)裂解的反应路径、选择性在邻近的B酸中心都与在孤立的酸中心上不同,显示出协同催化特点。其中,烷烃转化过程中裂解反应增加,脱氢反应减少,中间裂解产物相比于端基裂解产物具有更高的选择性。
