State Key Laboratory of Pollution Control and Resource Reuse, School of Environment, Nanjing University, Nanjing 210023, China.
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China.
Proc Natl Acad Sci U S A. 2023 Feb 28;120(9):e2217256120. doi: 10.1073/pnas.2217256120. Epub 2023 Feb 21.
Crystallographic control of crystals as catalysts with precise geometrical and chemical features is significantly important to develop sustainable chemistry, yet highly challenging. Encouraged by first principles calculations, precise structure control of ionic crystals could be realized by introducing an interfacial electrostatic field. Herein, we report an efficient in situ dipole-sourced electrostatic field modulation strategy using polarized ferroelectret, for crystal facet engineering toward challenging catalysis reactions, which avoids undesired faradic reactions or insufficient field strength by conventional external electric field. Resultantly, a distinct structure evolution from tetrahedron to polyhedron with different dominated facets of AgPO model catalyst was obtained by tuning the polarization level, and similar oriented growth was also realized by ZnO system. Theoretical calculations and simulation reveal that the generated electrostatic field can effectively guide the migration and anchoring of Ag precursors and free AgPO nuclei, achieving oriented crystal growth by thermodynamic and kinetic balance. The faceted AgPO catalyst exhibits high performance in photocatalytic water oxidation and nitrogen fixation for valuable chemicals production, validating the effectiveness and potential of this crystal regulation strategy. Such an electrically tunable growth concept by electrostatic field provides new synthetic insights and great opportunity to effectively tailor the crystal structures for facet-dependent catalysis.
通过精确的几何和化学特征来控制晶体作为催化剂的结晶,对于发展可持续化学具有重要意义,但也极具挑战性。受第一性原理计算的启发,通过引入界面静电场,可以实现离子晶体的精确结构控制。在此,我们报告了一种使用极化铁电体的高效原位偶极子源静电场调制策略,用于晶体面工程以实现具有挑战性的催化反应,该策略避免了传统外电场中不必要的法拉第反应或场强不足。结果,通过调节极化水平,AgPO 模型催化剂从四面体到多面体的明显结构演化得到了不同优势面的控制,同时在 ZnO 体系中也实现了类似的定向生长。理论计算和模拟表明,所产生的静电场可以有效地引导 Ag 前体和游离 AgPO 核的迁移和锚定,通过热力学和动力学平衡实现定向晶体生长。具有面的 AgPO 催化剂在光催化水氧化和固氮方面表现出高活性,用于有价值化学品的生产,验证了这种晶体调控策略的有效性和潜力。这种通过静电场进行电可调谐生长的概念为有效调控晶体结构以实现基于晶面的催化提供了新的合成思路和机会。