气体吸附诱导Cu(Au)合金中Au原子的偏聚和富集

合金中的表面成分和相偏析会改变其功能,尤其是在表面结构和化学起着至关重要作用的应用中.例如,合金催化剂的表面状态显著影响其在异相催化和电化学过程中的催化性能.表面成分偏析被认为是由表面能的差异驱动,以减少合金体系的总自由能.然而,目前合金中成分偏析的原子尺度进程还尚不清楚,尤其是对于气体分子诱导的成分偏析,在该过程中可能同时发生结构和化学重排.本文通过像差校正环境TEM从原子尺度研究了固溶态Cu(Au)合金在CO气氛下的表面偏析行为. CO气氛能够诱导Cu(Au)合金表面形成有序结构,在很大程度上改变合金的表面化学性质.高温条件下, CO气氛会进一步促进Au原子通过特定的"原子通道"进行扩散,在合金表面偏聚和富集.富集形成的Au纳米颗粒与合金表面在形貌和结构方面发生了丰富的动力学交互作用.这其中CO气体吸附也起着重要的作用.这些原子尺度的研究结果为双金属合金的表面偏析和去合金化机理提供了直接证据,并突出了气体吸附物在这些表面行为中的作用.

Gas adsorbate-induced Au atomic segregation and clustering from Cu(Au)

Surface compositional and phase segregation in an alloy can change its functionality, especially for applications where surface structure and chemistry play a vital role.For instance, the surface status of alloy catalysts significantly affects their catalytic performance for both heterogeneous and electrochemical processes. Surface segregation is believed to be driven by the difference in surface energy to reduce the total free energy of the alloy. However, the atomistic processes during the segregation process remain elusive, especially for gas molecule-induced segregation, where both structural and chemical reordering may occur. Herein, we achieved in-situ atomic-scale visualization of the surface segregation behaviors of a solid solution Cu(Au) alloy under the CO gas by an aberration-corrected environmental transmission electron microscope. CO-induced Cu(Au) surface ordering structures largely change the surface chemistry of the alloy. Further gas exposure at elevated temperature could facilitate Au atom diffusion through a specific "atomic channel" structure for dealloying and clustering on the surface. The segregated Au nanoparticles show rich phase and morphological dynamics interacting with the alloy surface, where the gas adsorption also plays an important role. These atomic insights provide direct evidence for the surface segregation and dealloying mechanisms of bimetallic alloys, and highlight the role of gas adsorbate in these surface processes.