1：Experimental Design and Method Selection:

The study involved synthesizing NiOx/TiO2 catalysts with various Ni loadings (1, 3, 5, and 10 wt.%) via impregnation and calcination. Thermo-photo catalytic hydrogen production was conducted in a gas-phase reactor with a SiO2 substrate for light-diffuse-reflection, using simulated AM 1.5G sunlight or visible light (λ>420 nm) at temperatures from 210 to 310°C. Isotope tracer experiments with D2O were performed to identify hydrogen sources.

2：5G sunlight or visible light (λ>420 nm) at temperatures from 210 to 310°C. Isotope tracer experiments with D2O were performed to identify hydrogen sources. Sample Selection and Data Sources:

2. Sample Selection and Data Sources: Catalysts were prepared using TiO2 (P25 from Macklin Co.) and Ni(NO3)2 solutions. Methanol-water mixtures (10% methanol) served as the sacrificial agent. Gas and liquid products were analyzed using gas chromatography (GC) and liquid chromatography (LC).

3：List of Experimental Equipment and Materials:

Equipment included a home-made quartz reactor, Xe lamp with AM1.5G filter, UVcut420 filter, high-pressure transfusion pump, electrical furnace, online gas chromatograph (GC) with TDX-01 column, liquid chromatograph (LC), scanning electron microscope (ZEISS Sigma 500), transmission electron microscope (FEI Tecnai G2 F20), X-ray diffractometer (Shimadzu XRD-6100), H2-TPR instrument (Tianjin Xianquan TP5076), UV-Vis spectrophotometer (Shimadzu UV-2600), XPS spectrometer (EscaLab 250Xi), infrared thermal imager (CEM DT-980H), electrochemical workstation for Mott-Schottky analysis, and mass spectrometer (MS) for isotope experiments.

4：5G filter, UVcut420 filter, high-pressure transfusion pump, electrical furnace, online gas chromatograph (GC) with TDX-01 column, liquid chromatograph (LC), scanning electron microscope (ZEISS Sigma 500), transmission electron microscope (FEI Tecnai G2 F20), X-ray diffractometer (Shimadzu XRD-6100), H2-TPR instrument (Tianjin Xianquan TP5076), UV-Vis spectrophotometer (Shimadzu UV-2600), XPS spectrometer (EscaLab 250Xi), infrared thermal imager (CEM DT-980H), electrochemical workstation for Mott-Schottky analysis, and mass spectrometer (MS) for isotope experiments. Experimental Procedures and Operational Workflow:

4. Experimental Procedures and Operational Workflow: The catalyst (15 mg) was dispersed on a SiO2 elliptic disk and placed in the reactor. After heating to the desired temperature, a methanol-water mixture (5 μL/min) and Ar gas (10 mL/min) were introduced. Light was turned on after stabilization, and gas products were analyzed periodically. For room temperature experiments, the catalyst was immersed in the mixture and illuminated.

5：Data Analysis Methods:

Hydrogen yields were measured via GC. Apparent quantum efficiencies were calculated based on light intensity, wavelength, and hydrogen evolution. Band structures were analyzed using Mott-Schottky plots and UV-Vis spectra. Isotope data were interpreted using mass spectrometry to determine hydrogen origins.