1：Experimental Design and Method Selection

A two-step solvothermal method was used to prepare hierarchical TiO2 microspheres composed of nanoparticle-decorated nanorods (NP-MS). The methodology included the synthesis of NP-MS, fabrication of DSSCs, and characterization of the materials and devices.

2：Sample Selection and Data Sources

The samples included NP-MS, MS (microspheres composed of nanorods), and P25 TiO2 nanoparticles. Data were obtained from SEM, TEM, XRD, UV-Vis spectroscopy, nitrogen adsorption–desorption isotherms, and electrochemical measurements.

3：List of Experimental Equipment and Materials

Equipment included SEM (S4800 HSD), TEM (Tecnai G2 F20), XRD (XRD-6000, Shimadzu), UV-Vis spectrometer (TU1901, Beijing Purkinje), Automated Surface Area & Pore Size Analyzer (ASAP 2020 V3.04H), and electrochemical workstation (VersaSTAT 3, Ametek, USA). Materials included tetrabutyl titanate, hydrochloric acid, TiCl4, toluene, isopropanol, diethylenetriamine, titanium isopropoxide, and N719 dye.

4：Experimental Procedures and Operational Workflow

The synthesis involved a two-step solvothermal method for NP-MS, followed by calcination. DSSCs were fabricated using the doctor blading method, and their performance was evaluated under illumination and dark conditions.

5：Data Analysis Methods

Data analysis included the use of the BJH method for pore size distribution, equivalent circuit modeling for EIS analysis, and calculation of electron lifetime and charge collection efficiency.