Zhengxin Ding

Conjugated microporous polymers (CMPs) have demonstrated considerable potential in the field of photocatalytic organic synthesis. However, the issue of intrinsic photogenerated carrier recombination severely limits their potential applications. Herein, a strategy for boosting the photocatalytic performance of CMP through the triboelectric effect is proposed. Specifically, the benzothiadiazole-involved CMP (BTTP) with inherent triboelectric character is processed into yolk-shell SiO2@BTTP materials, in which the BTTP and SiO2 function as tribo-negative and tribo-positive materials, respectively. The dual triboelectric effects occurring on both the internal and external surfaces of the shell are capable of inducing the formation of an additional built-in electric field within the BTTP photocatalyst, which effectively promotes the separation of photo-generated carriers, significantly enhancing photocatalytic performance. In the photocatalytic aerobic oxidation of the representative methyl phenyl sulfide, the yolk-shell SiO2@BTTP exhibits an ultrahigh sulfoxide yield of ∼399.6 mmol·g−1·h−1 under optimized conditions, accompanied by exceptional selectivity and cycling stability. Furthermore, this enhancement arising from the triboelectric effect is also observed in the selective photocatalytic oxidation of other organics by BTTP, including sulfide derivatives, benzyl alcohol and benzylamine. The findings of this work on utilizing intrinsic friction characteristics to boost the photocatalytic performance of CMP provide alternative avenues for the development of high-performance CMP-based photocatalysts, which will greatly unlock the application potential of such semiconductors in the field of artificial photosynthesis.

Photocatalytic oxidative coupling of methane is a promising route for methane valorization under mild conditions but remains limited by inefficient C−H activation and poor control over C−C coupling. Herein, we report an efficient Au/Ce1−In2O3 photocatalyst, in which substitutional Ce lattice doping and Au nanoparticle decoration cooperatively enable selective CH4 conversion to C2+ hydrocarbons. Ce incorporation tailors the local In−O lattice environment, enhancing CH4 adsorption, C−H dissociation, and stabilization of surface *CH3 intermediates. In contrast, Au nanoparticles serve as preferential sites for *CH3 coupling and controlled oxygen activation, enabling spatial separation of CH4 activation and C−C formation. As a result, Au/Ce1−In2O3 affords a high C2+ production rate of 4.53 × 103 μmol g−1 h−1 with 93% selectivity, together with sustained stability for 45 cycles and a turnover number of 2194. Mechanistic insights from in situ spectroscopies and density functional theory calculations unveil that Ce lattice doping directs the reaction pathway toward efficient C−C coupling. This work establishes lattice engineering as a powerful strategy for selective photocatalytic methane valorization.

Photocatalytic CO ₂ reduction using H ₂ O as the electron donor offers a sustainable pathway for carbon–neutral fuel synthesis; however, its efficiency is limited by sluggish charge separation and insufficient CO ₂ activation. Herein, we develop a ruthenium-decorated, fluorine-doped TiO ₂ photocatalyst (Ru/F-TiO ₂ ) that overcomes these limitations through spatially directed charge modulation and cooperative electronic engineering. Fluorine doping introduces oxygen vacancies that narrow the bandgap and form surface Ti‒F bonds, suppressing charge recombination. Simultaneously, Ru nanoparticles serve as efficient CO ₂ adsorption and activation centers while introducing additional surface defects that further strengthen CO ₂ binding. The strong coupling between Ru and semiconductor forms a Schottky junction, establishing a strong built-in electric field that promotes directional electron migration toward Ru sites and hole accumulation on F-TiO ₂ . Consequently, Ru/F-TiO ₂ exhibits outstanding activity and durability, delivering CO and CH ₄ production rates of 124.8 and 19.8 μmol/(g·h), respectively. In situ diffuse reflectance infrared Fourier-transform spectroscopy analysis reveals key proton-coupled, multi-electron intermediates, elucidating the reaction pathway. This study demonstrates that the synergistic integration of non-metal doping and metal cocatalyst engineering provides a powerful strategy to regulate charge dynamics and boost solar-driven CO ₂ conversion.

The heat transfer and storage are most crucial for the concentrated solar power (CSP) plants, and yet limited heavily by the thermal deactivation of calcium-looping materials. Here, we introduce air or O ₂ to on-site regenerate Al/Mn/Ce-co-doped CaO-looping materials operated at 800 ℃, sharply reducing the loss of energy storage density from 29.5% to 9.6% after 1000 cycles of thermochemical energy release and storage and holding a final energy storage density of ca. 1039 kJ kg ^− 1 at the 1000th cycle. Besides the slow phase separation of two formed heat-resistant compounds, Ca ₃ Al ₂ O ₆ and Ca ₂ MnO ₄ , from CaO matrix, the coverage of coke deposits deactivates the carbonation reaction beyond 500 cycles. The mechanistic studies reveal that the rich oxygen vacancies formed by Ce doping into Ca ₂ MnO ₄ NPs is mainly responsible for the formation of coke deposits on the surface of CaO NPs because they are thermodynamically favorable for directly splitting CO ₂ to C and O ₂ . These findings offer a practical guidance for on-site decoking of industrial Ca-looping process whether in the calcination step or the carbonation step, which is most imperative for reliably converting solar photon fluxes to dispatchable electricity in the next-generation CSP plants.

Ru/LaFeO ₃ functions as an efficient and durable catalyst for solar-driven methane dry reforming via a light-enhanced Mars-van Krevelen process..

Developing high‐performance Ca‐based materials that can work for long‐term heat transfer and storage in concentrated solar power plants is crucial to achieve the large‐scale conversion of solar photon fluxes to dispatchable electricity. This work demonstrates that a series of Mn, Zr co‐doped CaCO ₃ nanomaterials with the 3D ordered macroporous (3DOM) skeletons are successfully prepared by a novel strategy of templated metal salt co‐precipitation. The characterization results indicate that a majority of Zr and Mn are atomically dispersed into the highly‐crystallized CaCO ₃ framework, whereas a minor amount of Mn is present in the form of CaMnO ₃ nanoparticles (NPs). The optimal 3DOM material made by templating with PS microspheres with a diameter of ≈350 nm, 3DOM‐Ca80Mn10Zr10, shows a solar light absorptance of ≈74.1% and an initial energy storage density of 1706.4 kJ kg ⁻¹ . Importantly, it gives an impressive energy storage density loss of < 6.0% and maintains above 1600 kJ kg ⁻¹ after 125 cycles. The density functional theory calculations reveal that the co‐doping of Mn and Zr into the CaO crystal lattice offers a strong affinity to [Ca ₄ O ₄ ] clusters, as a result, the anti‐sintering of CaO NPs is significantly enhanced under high temperature.