Meidan Que,Peihong Ma,Yabo Wang,Yanbo Sun,Xiangwei Bai,Lili Gao,Jin Chen,Jian Wei,Hui Li
NH 2 -MIL-125 with abundant porosity and specific interactions with CO 2 molecules, has been demonstrate great potential in the field of photocatalytic CO 2 reduction. However, conventional NH 2 -MIL-125 and their composites much lower CO 2 photoreduction efficiency in aerobic environments because of the O 2 competition. To circumvent the issue, this study modifies NH 2 -MIL-125 through crystal facet engineering to enhance its selective CO 2 adsorption and photocatalytic efficiency in the environment of impurity CO 2 . The results indicate that NH 2 -MIL-125 featuring (101) crystal planes can sustain elevated catalytic activity in low-concentration CO 2 environments. In a pure CO 2 atmosphere, NM-5 achieves a CO production rate of 159.66 μmol·g −1 after 4 h, 1.85 times greater than the unmodified NH 2 -MIL-125. Under conditions simulating flue gas (5 % CO 2 ) and ultra-low CO 2 concentrations (0.15 % CO 2 ), NM-5 maintains CO production rates of 3.18 μmol·g −1 and 0.95 μmol·g −1 , respectively, representing 1.63 and 1.73 times the production rates of NM. Furthermore, theoretical calculations indicate that CO 2 exhibits a higher adsorption energy (−1.34 eV) compared to N 2 and O 2 (−0.67 eV and −0.15 eV) on the (101) crystal plane, which reveals the preferential adsorption of CO 2 on the (101) crystal planes. This study involves a novel strategy for optimizing MOFs crystal planes and provides significant insights into achieving efficient photocatalytic CO 2 reduction under aerobic conditions.
In this study, anatase TiO 2 nanorods with exposed high-energy {100} and {001} facets and low-energy {101} facets were fabricated in the presence of surfactants cetyltrimethylammonium bromide , didecyldimethylammonium bromide, and ammonia via a facile hydrothermal method without the erosive reagent hydrofluoric acid . The particle size and morphology were mainly tuned by regulating the hydrothermal temperature. When the temperature was increased from 150 °C to 180 °C and 200 °C, the length of the nanorods decreased from 700-1000 nm to 400–500 nm and 100–200 nm, respectively. Concurrently, the edges and tops of the truncated tetragonal pyramid of the TiO 2 nanorods became blurry and flattened. The synthesized typical TiO 2 nanorods were then used as photocatalysts , and their performance during the direct generation of H 2 from water was evaluated. The TiO 2 nanorods obtained at 150 °C successfully produced high amounts of H 2 evolution (281.36 μmol) in the presence of methanol as a sacrificial agent under ultraviolet light irradiation for 4 h. The outstanding photocatalytic activity of the nanorods was mainly ascribed to the formation of surface heterojunctions in the edges and corners between adjacent high-energy {001} or {100} facets and low-energy {101} facets. The formed heterojunctions could facilitate charge separation through preferential carrier flow toward the specific facets.
Aqueous zinc-ion batteries (AZIBs) offer promising safety and affordability, but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface. Herein, we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate (MMA). Exploiting its amphiphilic and functionally asymmetric architecture, MMA enables a coordinated interfacial reconstruction that disrupts Zn 2+ solvation in the outer Helmholtz plane, builds a chemisorbed coordination layer in the inner plane, and modulates local interfacial chemistry with spatial precision. This dual-region regulation collectively suppresses water reactivity, facilitates Zn 2+ desolvation, and drives crystallographically preferred deposition along the (101) plane, promoting lateral growth and mitigating dendrite formation. As a result, symmetric Zn||Zn cells exhibit over 4200 hours of stable cycling at 1 mA cm -2 and maintain 1100 hours of operation at 2 mA cm -2 , even at 0 °C. Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%, while Zn||NH 4 V 4 O 10 full cells deliver 93.92% capacity retention after 400 cycles at 2 A g -1 , and preserve 85.3% after 300 cycles at 0 °C. This work demonstrates a scalable, mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.
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