Hierarchically ordered oxides are of critical importance in material science and catalysis. Unfortunately, the design and synthesis of such systems remains a key challenge to realizing their potential. In this study, we demonstrate how the deposition of small oligomeric (MoO₃)_1–6 clusters—formed by the facile sublimation of MoO₃ powders—leads to the self-assembly of locally ordered arrays of immobilized mono-oxo (MoO₃)₁ species on anatase TiO₂(101). Using both high-resolution imaging and theoretical calculations, we reveal the dynamic behavior of the oligomers as they spontaneously decompose at room temperature, with the TiO₂ surface acting as a template for the growth of this hierarchically structured oxide. Transient mobility of the oligomers on both bare and (MoO₃)₁-covered TiO₂(101) areas is identified as key to the formation of a complete (MoO₃)₁ overlayer with a saturation coverage of one (MoO₃)₁ per two undercoordinated surface Ti sites. Simulations reveal a dynamic coupling of the reaction steps to the TiO₂ lattice fluctuations, the absence of which kinetically prevents decomposition. Further experimental and theoretical characterizations demonstrate that (MoO₃)₁ within this material are thermally stable up to 500 K and remain chemically identical with a single empty gap state produced within the TiO₂ band structure. Finally, we see that the constituent (MoO₃)₁ of this material show no proclivity for step and defect sites, suggesting they can reliably be grown on the (101) facet of TiO₂ nanoparticles without compromising their chemistry.

分层有序的氧化物在材料科学和催化中至关重要。不幸的是，此类系统的设计和合成仍然是实现其潜力的关键挑战。在本研究中，我们展示了小寡聚 (MoO ₃ ) _1-6簇（由 MoO ₃粉末容易升华形成）的沉积如何导致固定化单氧 (MoO ₃ )局部有序阵列的自组装锐钛矿型 TiO ₂ (101)上有_{1 个物种。}利用高分辨率成像和理论计算，我们揭示了低聚物在室温下自发分解时的动态行为，其中 TiO ₂表面充当这种分层结构氧化物生长的模板。低聚物在裸露和 (MoO ₃ ) ₁覆盖的 TiO ₂ (101) 区域上的瞬态迁移率被认为是形成完整的 (MoO ₃ ) ₁覆盖层的关键，其饱和覆盖率为每层 1 个 ( MoO ₃ ) ₁两个欠配位的表面Ti位点。_{模拟揭示了反应步骤与 TiO 2}晶格波动的动态耦合，缺乏这种耦合在动力学上会阻止分解。进一步的实验和理论表征表明，该材料中的 (MoO ₃ ) ₁在高达 500 K 的温度下具有热稳定性，并且在化学上与 TiO ₂能带结构内产生的单个空带隙状态保持相同。最后，我们发现该材料的成分 (MoO ₃ ) _{1没有表现出台阶和缺陷位点的倾向，这表明它们可以可靠地生长在 TiO 2}纳米颗粒的 (101) 面上，而不会影响其化学性质。