Spontaneous Imbibition in Nanomatrix-Fracture of Low Permeability Using Multiscale Nanofluidic Chips.

Spontaneous imbibition has garnered increasing attention as an attractive mechanism for developing tight reservoirs. Despite valuable insights from previous experiments, there remains a lack of understanding regarding the imbibition process within multiscale nanopore-fracture networks. In this work, we devised an innovative multiscale model incorporating over 105 nanochannels and integrating a microfracture network to explore the complex imbibition behavior in tight formations. Additionally, fracture-free nanomatrix models with low permeability were developed for comparative discussions. The results show that the Lucas-Washburn equation remains valid at the tremendous fracture-free nanopore networks under the confinement of 500 nm, with a relative deviation of ±6%. The nanomatrix's heterogeneity hinders the imbibition rate, resulting in a reduction of 4.6 to 10.8% in the imbibition slope. The viscosity plays a dominant role in the change of imbibition slope as temperature varies. Our experiments also found that the interactions between the nanomatrix and bulk fracture complicate the imbibition process. A single wetting front no longer applies in the nanomatrix-fracture networks. Differing fracture/microchannel connectivity leads to disparities in macroscopic patterns, saturation rates, and flow directions. The spatial arrangement of fractures significantly impacts the imbibition time. Overall, this work based on nanofluidic techniques systematically explores the effects of matrix heterogeneity, temperature, and fractures on the imbibition process. The real-time in situ visualization of fluid distribution in multiscale matrix-fracture systems has been achieved, which offers theoretical guidance for practical engineering applications.

Facet Engineering and Pore Design Boost Dynamic Fe Exchange in Oxygen Evolution Catalysis to Break the Activity-Stability Trade-Off.

The oxygen evolution reaction (OER) plays a vital role in renewable energy technologies, including in fuel cells, metal-air batteries, and water splitting; however, the currently available catalysts still suffer from unsatisfactory performance due to the sluggish OER kinetics. Herein, we developed a new catalyst with high efficiency in which the dynamic exchange mechanism of active Fe sites in the OER was regulated by crystal plane engineering and pore structure design. High-density nanoholes were created on cobalt hydroxide as the catalyst host, and then Fe species were filled inside the nanoholes. During the OER, the dynamic Fe was selectively and strongly adsorbed by the (101̅0) sites on the nanohole walls rather than the (0001) basal plane, and at the same time the space-confining effect of the nanohole slowed down the Fe diffusion from catalyst to electrolyte. As a result, a local high-flux Fe dynamic equilibrium inside the nanoholes for OER was achieved, as demonstrated by the Fe57 isotope labeled mass spectrometry, thereby delivering a high OER activity. The catalyst showed a remarkably low overpotential of 228 mV at a current density of 10 mA cm-2, which is among the best cobalt-based catalysts reported so far. This special protection strategy for Fe also greatly improved the catalytic stability, reducing the Fe leaching amount by 2 orders of magnitude compared with the pure Fe hydroxide catalyst and thus delivering a long-term stability of 130 h. An assembled Zn-air battery was stably cycled for 170 h with a low discharge/charge voltage difference of 0.72 V.

S and O Co-Coordinated Mo Single Sites in Hierarchically Porous Tubes from Sulfur-Enamine Copolymerization for Oxygen Reduction and Evolution.

The highly efficient bifunctional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is the key to achieving high-performance rechargeable Zn-air batteries. Non-precious-metal single-atom catalysts (SACs) have attracted intense interest due to their low cost and very high metal atomic utilization; however, high-activity bifunctional non-precious-metal SACs are still rare. Herein, we develop a new nanospace-confined sulfur-enamine copolymerization strategy to prepare a new type of bifunctional Mo SACs with O/S co-coordination (Mo-O2S2-C) supported on the multilayered, hierarchically porous hollow tubes. The as-prepared catalyst can not only expose more active sites and facilitate mass transfer due to their combined micropores, mesopores, and macropores but also have the S/O co-coordination structure for optimizing the adsorption energies of the ORR intermediates. Its ORR activity is among the highest, and it shows a low overpotential of 324 mV for the OER at 10 mA cm-2 in all of the reported Mo-based catalysts. When assembled in a Zn-air battery, it exhibits a high maximal power density of 197.3 mW cm-2 and a long service life of 50 hours, superior to those of Zn-air batteries using commercial Pt/C+IrO2.

Mesoporous Single Crystals with Fe-Rich Skin for Ultralow Overpotential in Oxygen Evolution Catalysis.

The oxygen evolution reaction (OER) is a key reaction in water splitting and metal-air batteries, and transition metal hydroxides have demonstrated the most electrocatalytic efficiency. Making the hydroxides thinner for more surface commonly fails to increase the active site number, because the real active sites are the edges. Up to now, the overpotentials of most state-of-the-art OER electrocatalysts at a current density of 10 mA cm-2 (η10 ) are still larger than 200 mV. Herein, a novel design of mesoporous single crystal (MSC) with an Fe-rich skin to boost the OER is shown. The edges around the mesopores provide lots of real active sites and the Fe modification on these sites further improves the intrinsic activity. As a result, an ultralow η10 of 185 mV is achieved, and the turnover frequency based on Fe atoms is as high as 16.9 s-1 at an overpotential of 350 mV. Moreover, the catalyst has an excellent catalytic stability, indicated by a negligible current drop after 10 000 cyclic voltammetry cycles. The catalyst enables Zn-air batteries to run stably over 270 h with a low charge voltage of 1.89 V. This work shows that MSC materials can provide new opportunities for the design of electrocatalysts.

Single-Atom Co Doped in Ultrathin WO3 Arrays for the Enhanced Hydrogen Evolution Reaction in a Wide pH Range.

Owing to the scarcity of Pt, low-cost, stable, and efficient nonprecious metal-based electrocatalysts that can be applied in a wide pH range for the hydrogen evolution reaction (HER) are urgently required. Herein, a highly efficient and robust HER catalyst that is applicable at all pH values is fabricated, containing isolated Co-single atomic sites anchored in the self-supported WO3 arrays grown on Cu foam. At a current density of 10 mA cm-2, the HER overpotentials are 117, 105, and 149 mV at pH values of 0, 7, and 14, respectively, which are significantly lower than those of the undoped WO3, suggesting superior electrocatalytic H2-evolution activity at all pH values. The catalyst also exhibits long-term stability over a wide pH range, particularly in an acidic medium over 24 h, owing to the excellent anticorrosion properties of WO3. Density functional theory calculations prove that the enhanced HER activity is attributed to the isolated Co sites because these optimize the adsorption energy of H* species on WO3. Moreover, the high electrical conductivity of Co-doped WO3 and the three-dimensional array structure supported on the porous metal support afford a catalyst with suitable HER kinetics to enhance the catalytic performance.