近日，北京工业大学-朱艺涵教授、阿德莱德大学-郑尧教授&乔世璋教授等人在JACS上发表重要文章，论文题为“Integrating Interactive Noble Metal Single-Atom Catalysts into Transition Metal Oxide Lattices”。贵金属具有广阔的催化应用前景，但受限于几种结构灵活性有限的填充模式。这里，作者通过将空间相关的贵金属单原子(例如，Pt、Pd和Ru)整合到过渡金属氧化物(TMOs，例如，Co3O4、Mn5O8、NiO、Fe2O3)的晶格中，实现了贵金属的几何结构多样化。所获得的贵金属单原子显示出与常规金属相不同的拓扑结构(例如，crs、fcu-hex-pcu、fcu和bcu-x)。例如，具有crs拓扑(Ptcrs-Co3O4的Pt单原子被赋予金属-金属和金属-载体相互作用的协同作用。建立了由TMO底物决定的各种Pt拓扑与其电催化活性之间的定量关系。作者预计，这种类型的相互作用的单原子催化剂可以弥合“紧密堆积”的纳米粒子和孤立的单原子之间的几何、拓扑和电子结构差距，作为两种常见的多相催化剂。
Figure 1. Structural prediction and identification of various noble metal-substituted TMOs. (a-d) Projected ternary phase diagrams of Ptsubstituted TMOs for (a) Pt-Co-O, (b) Pt-Mn-O, (c) Pt-Ni-O, and (d) Pt-Fe-O in the (Aμpυ AμtM) planes. Orange regions represent the existence of stable Pt-CoO16 Pt-Mn,O1 Pt-NisO16 and Pt-FeO18- (e) XRD patterns of Pt-substituted TMOs including Pt-Co,O, (Co0PDF#42-1467), Pt-NiO (NiO: PDF#47-1049), Pt-MngOs (MngOg: PDF#39-1218), Pt-FeO (FeO: PDF#33-0664), Pt-ZnO (ZnO: PDF#361451), and Pt-CuO (CuO: PDF#65-2309).
Figure 2. Structural identification of Pt-TMOs. (a) DRIFT spectra on CO adsorbed various catalysts. Three sets of bands illustrated by the blue (~2200 cm-'), gray (~2115 cm-'), and orange (~2065 cm-!) areas refer to CO adsorption on TMO hosts, isolated Pt single atoms, and correlated Pt sites, respectively. (b) Wavelet transform edge extended X-ray absorption fine structure (WT-EXAFS) spectra of various catalysts. Hybrid samples show three intensity maxima at around k = 4.0, 6.0-7.0 to 8.5-10.0 A-', which can be, respectively, ascribed to the Pt-O, Pt-TM (TM = Co/Mn/Ni/Fe), and Pt-Pt scatterings.
Figure 3. Topological diversification of correlated Pt sites. From top to bottom: the topology models, HRSTEM images with Pt sites marked with yellow circles, simulated 22 maps, and structure models of the corresponding red dashed rectangular areas in the images at the top of (a) Pt-CoO, (b) Pt-MnsOg, (c) Pt-NiO, and (d) Pt-FeO3, respectively. Correlated Pt sites that formed polyhedrons in the topology models are rendered in light green. Two sets of cationic sublattices of Co cations in Pt-CosO4 were rendered in two different colors, referring to crs and dia underlying topologies. Three sets of cationic sublattices of Mn cations in Pt-MnsOs are rendered in different colors, which refer to fcu, hex, and peu underlying topologies. Cationic sublattices of Pt-NiO and Pt-FezO3 hybrid structures are assigned to feu and bcu-x nets, respectively. Corresponding zone axes of these HRSTEM images for CosO4, MngOg, NiO, and FezO3 are [233], [472], [121], and [8 10 1] respectively.
Figure 6. Structure-property relationship of Pt-TMO catalysts. (a) Calculated values of ICOHP for Pt-TMO structures, which indicate the strength of Pt-Pt interactions. Each data point represents an ICOHP value between each Pt atoms in a structure model with three Pt substitutions as shown in Figure S22. Pt-TMO structures demonstrate a widely extended ICOHP ranges in comparison with those of conventional Pt metal and Pt alloys. (b) Tafel plots of PtTMO catalysts (solid curves) and fitting lines to the Butler-Volmer equation (dashed curves). (c) Relationship between the experimentally determined jo on Pt-CoO4, Ptfcu-her-pcu-MngOg, Pt-NiO,Ptbcu-r-FeO3, and Pt/C and the corresponding AG values on PtTMO models with two Pt substitutions and Pt(111). (d) Mainly the linear relationship between AG. values and the d-band center of the Pt-TM domain containing a central Pt atom and the nearest neighboring TM/Pt sites on Pt-TMO models with two Pt substitutions.
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球差电镜 | 有限元模拟 | 理论计算
原位XRD、原位Raman、原位FTIR、原位TEM
加急测试
刘老师
研图汇技术经理
182 6975 5918
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