Peng Wei, Han Jiuhui, Lu Ying-Rui, Luo Min, Chan Ting-Shan, Peng Ming, Tan Yongwen
Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan.
National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan.
ACS Nano. 2022 Mar 22;16(3):4116-4125. doi: 10.1021/acsnano.1c09841. Epub 2022 Feb 21.
Two-dimensional (2D) MXenes have been developed to stabilize single atoms via various methods, such as vacancy reduction and heteroatom-mediated interactions. However, anchoring single atoms on 3D porous MXenes to further increase catalytic active sites and thus construct electrocatalysts with high activity and stability remains unexplored. Here, we reported a general synthetic strategy for engineering single-metal sites on 3D porous N, P codoped TiCT nanosheets. Through a "gelation-and-pyrolysis" process, a series of atomically dispersed metal catalysts (Pt, Ir, Ru, Pd, and Au) supported by N, P codoped TiCT nanosheets with 3D porous structure can be obtained and serve as efficient catalysts for the electrochemical hydrogen evolution reaction (HER). As a result of the favorable electronic and geometric structure of N(O), P-coordinated metal atoms optimizing catalytic intermediates adsorption and 3D porous structure exposing the active surface sites and facilitating charge/mass transfer, the as-synthesized Pt SA-PNPM catalyst shows ∼20-fold higher activity than the commercial Pt/C catalyst for electrochemical HER over a wide pH range.
二维（2D）MXenes已通过各种方法开发出来，用于稳定单原子，例如空位还原和杂原子介导的相互作用。然而，将单原子锚定在三维多孔MXenes上以进一步增加催化活性位点，从而构建具有高活性和稳定性的电催化剂，这一领域仍未得到探索。在此，我们报道了一种在三维多孔氮、磷共掺杂TiCT纳米片上设计单金属位点的通用合成策略。通过“凝胶化-热解”过程，可以获得一系列由具有三维多孔结构的氮、磷共掺杂TiCT纳米片负载的原子分散金属催化剂（铂、铱、钌、钯和金），并用作电化学析氢反应（HER）的高效催化剂。由于氮（氧）、磷配位的金属原子具有良好的电子和几何结构，优化了催化中间体的吸附，且三维多孔结构暴露了活性表面位点并促进了电荷/质量转移，因此合成的Pt SA-PNPM催化剂在很宽的pH范围内对电化学HER的活性比商业Pt/C催化剂高约20倍。
