Mesoporous TiO2 has gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Herein, we report the facile synthesis of ordered mesoporous black TiO2 (OMBT) materials, which exhibit excellent photocatalytic hydrogen evolution performances. In this case, the employment of a thermally stable and high-surface-area mesoporous TiO2 as the hydrogenation precursor is the key for fabricating the OMBT materials, which not only facilitate H2 gas diffusion into TiO2 and interaction with their structures but also maintain the ordered mesoporous structures as well as inhibit the phase transformation (from anatase to rutile) and crystal growth during hydrogenation at 500 °C. The resultant OMBT materials possess a relatively high surface area of ∼124 m(2) g(-1) and a large pore size and pore volume of ∼9.6 nm and 0.24 cm(3) g(-1), respectively. More importantly, the OMBT materials can extend the photoresponse from ultraviolet to visible and infrared light regions and exhibit a high solar-driven hydrogen production rate (136.2 μmol h(-1)), which is almost two times as high as that of pristine mesoporous TiO2 (76.6 μmol h(-1)).

Thermally-stable, ordered mesoporous anatase TiO 2 with large pore size and high crystallinity has been successfully synthesized through an evaporationinduced self-assembly technique, combined with encircling ethylenediamine (EN) protectors to maintain the liquid crystal mesophase structure of TiO 2 primary particles, followed by calcination at higher temperature. The structures of the prepared mesoporous TiO 2 are characterized in detail by small-angle and wide-angle X-ray diffraction, Raman spectra, N 2 adsorption/ desorption isotherms, and transmission electron microscopy. Experimental results indicate that the well-ordered mesoporous structure could be maintained up to 700 ° C (M700) and also possesses large pore size (10 nm), high specifi c BET surface area (122 m 2 g − 1 ), and high total pore volumes (0.20 cm 3 g − 1 ), which is attributed to encircling EN protectors for maintaining the mesoporous framework against collapsing, inhibiting undesirable grain growth and phase transformation during the calcination process. A possible formation mechanism for the highly stable large-pore mesoporous anatase TiO 2 is also proposed here, which could be further confi rmed by TG/FT-IR in site analysis and X-ray photoelectron spectroscopy. The obtained mesoporous TiO 2 of M700 exhibit better photocatalytic activity than that of Degussa P25 TiO 2 for degradation of highly toxic 2,4-dichlorophenol under UV irradiation. This enhancement is attributed to the well-ordered large-pore mesoporous structure, which facilitates mass transport, the large surface area offering more active sites, and high crystallinity that favors the separation of photogenerated electron-hole pairs, confi rmed by surface photovoltage spectra.

Photocatalytic hydrogen production using semiconductors is identified as one of the most promising routes for sustainable energy; however, it is challenging to harvest the full solar spectrum in a particulate photocatalyst for high activity. Herein, a hierarchical hollow black TiO2/MoS2/CdS tandem heterojunction photocatalyst, which allows broad‐spectrum absorption, thus delivering enhanced hydrogen evolution performance is designed and synthesized. The MoS2 nanosheets not only function as a cost‐effective cocatalyst but also act as a bridge to connect two light‐harvesting semiconductors into a tandem heterojunction where the CdS nanoparticles and black TiO2 spheres absorb UV and visible light on both sides efficiently, coupling with the MoS2 cocatalyst into a particulate photocatalyst system. Consequently, the photocatalytic hydrogen rate of the black TiO2/MoS2/CdS tandem heterojunction is as high as 179 µmol h−1 per 20 mg photocatalyst under visible‐light irradiation, which is almost 3 times higher than that of black TiO2/MoS2 heterojunctions (57.2 µmol h−1). Most importantly, the stability of CdS nanoparticles in the black TiO2/MoS2/CdS tandem heterojunction is greatly improved compared to MoS2/CdS because of the formation of tandem heterojunctions and the strong UV‐absorbing effect of black TiO2. Such a tandem architectural design provides new ways for synthesizing particulate photocatalysts with high efficiencies.