Pd-Rh nanoparticles are known to easily undergo surface restructuring in reactive environment. This study quantifies, with the help of density functional(DFT) calculations and a novel topological approach, atomic orde...Pd-Rh nanoparticles are known to easily undergo surface restructuring in reactive environment. This study quantifies, with the help of density functional(DFT) calculations and a novel topological approach, atomic ordering and surface segregation effects in Pd-Rh particles with compositions 1:3, 1:1 and 3:1 containing up to 201 atoms(ca. 1.7 nm). The obtained data are used to reliably optimise energetically preferred atomic orderings in inaccessible by DFT Pd-Rh particles containing thousands of atoms and exhibiting sizes exceeding 5 nm, which are typical for catalytic metal particles. It is outlined, how segregation effects on the surface arrangement of Pd-Rh nanoalloy catalysts induced by adsorbates can be evaluated in a simple way within the present modelling setup.展开更多
铂耗和氨耗是硝酸生产的主要技术指标。在流动氧气氛模拟条件下,以及800~950℃的硝酸生产实际氨氧化环境中,Pt-Rh二元和Pt-Pd-Rh三元合金及其催化网的失重和铂耗均遵循相同的模式,即ΔW/S=Kt2/3与ΨΣ=K't2/3。工厂实际测定数据表明...铂耗和氨耗是硝酸生产的主要技术指标。在流动氧气氛模拟条件下,以及800~950℃的硝酸生产实际氨氧化环境中,Pt-Rh二元和Pt-Pd-Rh三元合金及其催化网的失重和铂耗均遵循相同的模式,即ΔW/S=Kt2/3与ΨΣ=K't2/3。工厂实际测定数据表明,在常压氨氧化法生产硝酸过程中,Pt-12Pd-3.5Rh合金催化网的铂耗为0.044 g Pt/t(HNO3),比Pt-4Pd-3.5Rh合金催化网的铂耗(0.061g Pt/t(HNO3))低28%;在中压氨氧化法生产硝酸过程中,Pt-12Pd-3.5Rh合金催化网的铂耗为0.121g Pt/t(HNO3),比Pt-5Rh和Pt-10Rh合金催化网的铂耗(0.15~0.153 g Pt/t(HNO3))低21%,而其氨耗比后者降低3%~7%。研究结果证明,在Pt-Rh合金中添加钯或在Pt-Pd-Rh合金中增加钯含量明显降低催化合金的铂耗。展开更多
基金supported by the National Natural Science Foundation of China(20773090,20803049)Specialized Research Fund for the Doctoral Program of Higher Education,China(20070610026)~~
基金financed by the Generalitat de Catalunya via a pre-doctoral grant 2018FI-B-00384the Operational program“Science and Education for Smart Growth”,project BG05M2OP001-2.009-0028 for funding his research stay in the University of Barcelona+2 种基金financial support by the Bulgarian Ministry of Education and Science under the National Research Programme“Low-carbon Energy for the Transportsupport by the Spanish grants PGC2018-093863-B-C22,CTQ2015-64618-RMDM-2017-0767 as well as by the grant 2017SGR13 of the Generalitat de Catalunya
文摘Pd-Rh nanoparticles are known to easily undergo surface restructuring in reactive environment. This study quantifies, with the help of density functional(DFT) calculations and a novel topological approach, atomic ordering and surface segregation effects in Pd-Rh particles with compositions 1:3, 1:1 and 3:1 containing up to 201 atoms(ca. 1.7 nm). The obtained data are used to reliably optimise energetically preferred atomic orderings in inaccessible by DFT Pd-Rh particles containing thousands of atoms and exhibiting sizes exceeding 5 nm, which are typical for catalytic metal particles. It is outlined, how segregation effects on the surface arrangement of Pd-Rh nanoalloy catalysts induced by adsorbates can be evaluated in a simple way within the present modelling setup.
基金Key Research and Development Program of Sichuan Science and Technology Department(2019YFS0513)National Natural Science Foundation of China(21962021)。
文摘铂耗和氨耗是硝酸生产的主要技术指标。在流动氧气氛模拟条件下,以及800~950℃的硝酸生产实际氨氧化环境中,Pt-Rh二元和Pt-Pd-Rh三元合金及其催化网的失重和铂耗均遵循相同的模式,即ΔW/S=Kt2/3与ΨΣ=K't2/3。工厂实际测定数据表明,在常压氨氧化法生产硝酸过程中,Pt-12Pd-3.5Rh合金催化网的铂耗为0.044 g Pt/t(HNO3),比Pt-4Pd-3.5Rh合金催化网的铂耗(0.061g Pt/t(HNO3))低28%;在中压氨氧化法生产硝酸过程中,Pt-12Pd-3.5Rh合金催化网的铂耗为0.121g Pt/t(HNO3),比Pt-5Rh和Pt-10Rh合金催化网的铂耗(0.15~0.153 g Pt/t(HNO3))低21%,而其氨耗比后者降低3%~7%。研究结果证明,在Pt-Rh合金中添加钯或在Pt-Pd-Rh合金中增加钯含量明显降低催化合金的铂耗。
