Xie Minghao, Zhang Bowen, Jin Zhaoyu, Li Panpan, Yu Guihua
Materials Science and Engineering Program and Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, United States.
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, P.R. China.
ACS Nano. 2022 Sep 27;16(9):13715-13727. doi: 10.1021/acsnano.2c05190. Epub 2022 Aug 10.
As an emerging class of materials with distinctive physicochemical properties, metallenes are deemed as efficient catalysts for energy-related electrocatalytic reactions. Engineering the lattice strain, electronic structure, crystallinity, and even surface porosity of metallene provides a great opportunity to further enhance its catalytic performance. Herein, we rationally developed a reconstruction strategy of Pd metallenes at atomic scale to generate a series of nonmetallic atom-intercalated Pd metallenes (M-Pdene, M = H, N, C) with lattice expansion and S-doped Pd metallene (S-Pdene) with an amorphous structure. Catalytic performance evaluation demonstrated that N-Pdene exhibited the highest mass activities of 7.96 A mg, which was 10.6 and 8.5 time greater than those of commercial Pd/C and Pt/C, respectively, for methanol oxidation reaction (MOR). Density functional theory calculations suggested that the well-controlled lattice tensile strain as well as the strong p-d hybridization interaction between N and Pd resulted in enhanced OH adsorption and weakened CO adsorption for efficient MOR catalysis on N-Pdene. When tested as hydrogen evolution reaction (HER) catalysts, the amorphous S-Pdene delivered superior activity and durability relative to the crystalline counterparts because of the disordered Pd surface with a further elongated bond length and a downshifted d-band center. This work provides an effective strategy for atomic engineering of metallene nanomaterials with high performance as electrocatalysts.
作为一类具有独特物理化学性质的新兴材料，金属烯被认为是能量相关电催化反应的高效催化剂。调控金属烯的晶格应变、电子结构、结晶度乃至表面孔隙率，为进一步提升其催化性能提供了绝佳机遇。在此，我们合理开发了一种原子尺度的钯金属烯重构策略，以生成一系列具有晶格膨胀的非金属原子插层钯金属烯（M-Pdene，M = H、N、C）以及具有非晶结构的硫掺杂钯金属烯（S-Pdene）。催化性能评估表明，对于甲醇氧化反应（MOR），N-Pdene展现出最高质量活性，为7.96 A mg，分别是商业Pd/C和Pt/C的10.6倍和8.5倍。密度泛函理论计算表明，良好控制的晶格拉伸应变以及N与Pd之间强烈的p-d杂化相互作用，导致N-Pdene上OH吸附增强而CO吸附减弱，从而实现高效的MOR催化。当作为析氢反应（HER）催化剂进行测试时，非晶态的S-Pdene相对于晶体对应物表现出优异的活性和耐久性，这归因于其无序的Pd表面具有进一步拉长的键长和下移的d带中心。这项工作为高性能金属烯纳米材料作为电催化剂的原子工程提供了一种有效策略。
