Xin Yu

Zirconium-based nanomaterials have emerged as an appealing family of semiconductor photocatalysts, thanks to their distinctive physicochemical properties including excellent chemical stability and tunable band structures. Even so, their photocatalytic performance is often constrained by intrinsic flaws in electronic configuration and microstructure. To overcome these drawbacks, a variety of modification strategies have been developed and rationally tailored for zirconium-based photocatalysts over recent years, achieving significant enhancements in their photocatalytic performance and durability. Despite these remarkable advancements, the core mechanisms governing the substantial improvement of photocatalytic performance remain inadequately explored and lack comprehensive elucidation. In this review, we provide a comprehensive overview of zirconium-based nanomaterials for advanced photocatalysis, with a focus on their synthetic routes, modification strategies, and practical applications. We also present an analysis of advanced characterizations and theoretical calculations for mechanism interpretation, aiming to establish the design paradigms and robust theoretical foundations for rational fabrication of zirconium-based photocatalysts.

To address the bottlenecks of low visible-light utilization, rapid carrier recombination, and insufficient active sites of pristine photocatalysts for contaminant degradation, step-scheme (S-scheme) g-C ₃ N ₄ /Zn-Sr _0.25 H _1.5 Ta ₂ O ₆ ·H ₂ O photocatalysts were synthesized via a combined calcination-solvothermal method. The photocatalytic performance towards tetracycline degradation and enhancement mechanism were systematically explored by integrating multiple characterization techniques. The synthesized g-C ₃ N ₄ /Zn-Sr _0.25 H _1.5 Ta ₂ O ₆ ·H ₂ O composites exhibited improved photocatalytic performance, with a maximum apparent rate constant (k) of 0.12269 min ^-1 , 3.69, 38.22, and 2.65 times those of Sr _0.25 H _1.5 Ta ₂ O ₆ ·H ₂ O, g-C ₃ N ₄ , and binary g-C ₃ N ₄ /Sr _0.25 H _1.5 Ta ₂ O ₆ ·H ₂ O, respectively. This work systematically deciphered the synergistic mechanism between Zn-doping and S-scheme heterojunction, as probed by in-situ X-ray photoelectron spectroscopy (XPS) measurements that directly demonstrated the directional migration of photogenerated carriers. Zn-doping broadened the optical absorption and created more active sites for tetracycline adsorption and surface degradation reaction, while the constructed S-scheme heterostructures effectively promoted the separation and directional migration of photogenerated carriers for tetracycline degradation. This study not only provides novel theoretical insights and experimental references for the precise design and controllable synthesis of element-doped S-scheme heterojunctions but also offers a promising strategy for environmental remediation of refractory organic pollutants.

In the catalytic cracking of naphtha to light olefins over conventional microporous ZSM-5 zeolite, issues such as high mass-transfer resistance leading to low conversion and high acid-site density causing olefin consumption are commonly encountered. In this work, a hierarchical nanosponge ZSM-5 zeolite (NP) with a Si/Al ratio of 20 was synthesized. Acid washing was applied to reduce the acid-site density and introduce defects (NP-Aci). Furthermore, extra-framework Al was introduced via impregnation to modify the defective hierarchical-porous ZSM-5 (Al/NP-Aci). Characterization results confirm that the impregnated Al is anchored at defect sites, existing as extra-framework Al that acts as a Lewis acid. In n-pentane cracking, the Lewis-acid-modified Brønsted acid sites promote the monomolecular cracking of n-pentane, while the lowered acid density suppresses the bimolecular hydrogen transfer of the olefins. At 600 °C, the Al/NP-Aci catalyst achieves 98.03% n-pentane conversion, with ethylene and propylene selectivity of 30.12% and 19.63%, respectively. Moreover, the Al/NP-Aci catalyst exhibits excellent cracking stability, showing a deactivation rate of only 3.81% after 16 h of reaction at 600 °C under a weight hourly space velocity (WHSV) of 6.26 h–1.

Cyclohexanone serves as a crucial precursor in the chemical industry and can be produced via selective hydrogenation of phenol, a process that suffers from sluggish reaction kinetics and over‐hydrogenation to cyclohexanol. This study develops a hierarchical ZSM‐5 zeolite‐supported Pd–Co bimetallic catalyst (Pd–Co/DZ) that addresses this dichotomy through a synergistic dual‐function design. Compared with monometallic Pd, the formation of highly dispersed Pd–Co alloy substantially enhances the adsorption and activation rate of H ₂ , thereby accelerating the phenol hydrogenation. The hierarchical zeolite exploits its abundant surface defect sites to chelate Co species, generating Co–O–Si bonds. This configuration promotes the tilted adsorption of phenol while suppressing the deep hydrogenation of cyclohexanone to cyclohexanol. Leveraging the dual role of Co in the Pd/ZSM‐5 under a phenol‐to‐Pd molar ratio of 1132, a turnover frequency of 268.9 h ⁻¹ for phenol‐to‐cyclohexanone with 93.1% yield is achieved. This work provides valuable insights for the design of catalysts in the hydrogenation of phenolics.

Solar light‐driven photocatalytic hydrogen generation from seawater can enable sustainable fuel conversion and contribute to decarbonizing energy systems. However, seawater photocatalysis still faces inherent efficiency bottlenecks that demand further exploration. This work develops grain‐like Zr ³⁺ ‐ZrO ₂ and Pt single atom (Pt SA)‐modified step scheme (S‐scheme) Zr ³⁺ ‐ZrO ₂ @g‐C ₃ N ₄ heterostructures for seawater hydrogen generation under visible‐light irradiation. Experimental results demonstrate that the synthesized Pt SA/Zr ³⁺ ‐ZrO ₂ @g‐C ₃ N ₄ heterostructures markedly enhanced charge separation and substantially boosted seawater photocatalytic hydrogen production, due to synergistic Pt SA effects and S‐scheme electron transfer pathways. The Pt SA/Zr ³⁺ ‐ZrO ₂ @g‐C ₃ N ₄ heterojunction achieved a maximum hydrogen evolution rate of approximately 15683.80 µmol g ⁻¹ , which was 4.68 times of Pt NPs/Zr ³⁺ ‐ZrO ₂ @g‐C ₃ N ₄ heterojunction, 9.16 times of Pt NPs/g‐C ₃ N ₄ , and 1041.97 times of Pt NPs/Zr ³⁺ ‐ZrO ₂ sample, and maintained a good photocatalytic hydrogen generation performance even after five photocatalytic hydrogen evolution cycles. Turnover number (TON) and turnover frequency (TOF) were approximately 105.19 and 35.06 h ⁻¹ , respectively. Finally, a plausible S‐scheme charge transfer mechanism of Pt SA/Zr ³⁺ ‐ZrO ₂ @g‐C ₃ N ₄ heterojunction was suggested for hydrogen generation from seawater splitting.