Phase-tunable mesoporous nickel phosphides are promising electrocatalysts for alkaline hydrogen evolution. Their catalytic behavior can be regulated by Ni/P stoichiometry and accessible mesoporous architectures. However, simultaneously controlling phosphide phase evolution while maintaining an open mesoporous framework remains challenging, as high-temperature phosphidation often causes framework shrinkage, pore collapse, and uncontrolled phase transformation. Herein, we report a charge-mediated cooperative assembly strategy for the one-pot synthesis of mesoporous Ni_xP_y with tunable crystalline phases. In this system, CTAC-derived CTA⁺ micelles, phosphate species, and Ni–citrate complexes cooperatively assemble into inorganic–organic composite micelle precursors through electrostatic interactions and hydrogen bonding. Dynamic light scattering, zeta-potential analysis, and Fourier transform infrared spectroscopy support an S⁺X⁻I-type cooperative assembly pathway, in which CTA⁺ micelles, phosphate species, and Ni–citrate complexes act as structure-directing agents, charge-mediating/hydrogen-bonding linkers, and inorganic precursor units, respectively. By regulating the NH₄H₂PO₄ dosage, the effective phosphorus supply can be precisely adjusted, enabling a stepwise phase evolution from Ni₃P to Ni₁₂P₅ and ultimately to Ni₂P while preserving the well-defined mesoporous framework. The optimized mesoporous Ni₂P-1.0 catalyst requires an overpotential of 48 mV to reach 10 mA cm⁻², exhibits a Tafel slope of 67 mV dec⁻¹, and maintains stable operation for 100 h in 1.0 M KOH. These findings establish a practical route for coupling phase regulation with mesostructure engineering in transition-metal phosphides and offer guidance for designing efficient noble-metal-free electrocatalysts toward alkaline hydrogen evolution.

Porous perovskite metal oxides (PPMOs) have emerged as promising candidates for efficient catalysts in fine chemical engineering due to their flexible crystal structures and tunable surface chemical properties. However, the conventional high temperature calcination process required for crystallization frequently leads to collapse of pore structure, limiting the practical application of PPMOs. Herein, we propose a facile and general polymer derived bubble templates strategy to synthesize a series of PPMOs, including single-component PPMOs (e.g., LaMnO₃, LaFeO₃, LaCoO₃, PrMnO₃, and NdMnO₃) and multiple-component PPMOs (e.g., LaCo_xMn_1−xO₃ (x = 0.1, 0.2, and 0.3)) with tunable pore structure. The pore architectures (macropores, hierarchically meso/macropores, and mesopores), pore sizes, and specific surface areas (14–40 m²·g⁻¹) of the samples can be precisely tailored by adjusting the sizes of bubble templates. The hierarchically meso/macroporous LaMnO₃ features multiple structural advantages, including well-defined hierarchical porous architecture, high specific surface area, and abundant oxygen vacancies, and exhibits a remarkable catalytic performance in oxidation of benzyl alcohol to benzaldehyde, with conversion and selectivity of 99% and 99%, respectively. This work not only provides a scalable and versatile pathway for fabricating advanced porous materials but also offers new perspectives for their application in diverse catalytic processes.

Nowadays, multi-shelled mesoporous hollow metal oxide nanospheres have drawn a lot of attention due to their large internal space, nanometer scaled shell thickness, high specific surface area and well-defined mesopores, of which unique nanostructure endows metallic oxides with enhanced properties. In this thesis, we have studied and proposed a versatile ligand-assisted cooperative template method to synthesize multi-shelled mesoporous hollow metal hydroxides and oxides nanospheres, in which silica nanospheres act as sacrificial templates and the coordination interaction between metal ions and surfactant can be cooperatively amplified by using chelating ligand (ascorbic acid) as a co-template. The synthesized metal hydroxides and oxides nanospheres possess stable hollow structure, uniform spherical morphology and tunable diameter from 270 to 690 nm. All the multi-shelled mesoporous hollow metal hydroxide and metal oxide nanospheres exhibit high surface areas (up to 640 m²/g). The obtained Au nanoparticles loaded composited nanospheres exhibit excellent reactivity for solvent-free aerobic oxidation of ethylbenzene with high activity (28.2%) and selectivity (87%).