Solar-driven interfacial evaporation (SDIE) is a highly promising approach to achieve sustainable desalination and tackle the global freshwater crisis. Despite advancements in this field, achieving balanced thermal localization and salt resistance remains a challenge. Herein, the study presents a 3D hierarchical porous ceramic platform for SDIE applications. The utilized alumina foam ceramics (AFCs) exhibit remarkable corrosion resistance and chemical stability, ensuring a prolonged operational lifespan in seawater or brines. The millimeter-scale air-filled pores in AFCs prevent thermal losses through conduction with bulk water, resulting in heat-localized interfaces. The hydrophilic nature of macroporous AFC skeletons facilitates rapid water replenishment on the evaporating surface for effective salt-resistant desalination. Benefiting from its self-radiation adsorption and side-assisted evaporation capabilities, the AFC-based evaporators exhibit high indoor evaporation rates of 2.99 and 3.54 kg m-2 h-1 under one-sided and three-sided illumination under 1.0 sun, respectively. The AFC-based evaporator maintains a high evaporation rate of ≈2.77 kg m-2 h-1 throughout the 21-day long-term test. Furthermore, it achieves a daily water productivity of ≈10.44 kg m-2 in outdoor operations. This work demonstrates the potential of 3D hierarchical porous ceramics in addressing the trade-off between heat localization and salt resistance, and contributes to the development of durable solar steam generators.
Developing robust and cost-effective electrocatalysts to boost hydrogen evolution reactions (HERs) and oxygen evolution reactions (OERs) is crucially important to electrocatalytic water splitting. Herein, bifunctional electrocatalysts, by coupling Co nanoparticles and N-doped carbon nanotubes/graphitic nanosheets (Co@NCNTs/NG), were successfully synthesized via facile high-temperature pyrolysis and evaluated for water splitting. The morphology and particle size of products were influenced by the precursor type of the cobalt source (cobalt oxide or cobalt nitrate). The pyrolysis product prepared using cobalt oxide as a cobalt source (Co@NCNTs/NG-1) exhibited the smaller particle size and higher specific surface area than that of the pyrolysis products prepared using cobalt nitrate as a cobalt source (Co@NCNTs/NG-2). Notably, Co@NCNTs/NG-1 displayed much lower potential -0.222 V vs. RHE for HER and 1.547 V vs. RHE for OER at the benchmark current density of 10 mA cm-2 than that of Co@NCNTs/NG-2, which indicates the higher bifunctional catalytic activities of Co@NCNTs/NG-1. The water-splitting device using Co@NCNTs/NG-1 as both an anode and cathode demonstrated a potential of 1.92 V to attain 10 mA cm-2 with outstanding stability for 100 h. This work provides a facile pyrolysis strategy to explore highly efficient and stable bifunctional electrocatalysts for water splitting.
Lithium (Li) metal has been regarded as the "Holy Grail" of Li battery anodes thanks to its high theoretic specific capacity and low reduction potential, but uneven formation of Li dendrites and uncontrollable Li volume changes hinder the practical applications of Li metal anodes. A three-dimensional (3D) current collector is one of the promising strategies to address the above issues if it can be compatible with current industrialized process. Here, Au-decorated carbon nanotubes (Au@CNTs) are electrophoretically deposited on commercial Cu foil as a 3D lithiophilic skeleton to regulate Li deposition. The thickness of the as-prepared 3D skeleton can be accurately controlled by adjusting the deposition time. Benefitting from the reduced localized current density and improved Li affinity, the Au@CNTs-deposited Cu foil (Au@CNTs@Cu foil) achieves uniform Li nucleation and dendrite-free Li deposition. Compared with bare Cu foil and CNTs deposited Cu foil (CNTs@Cu foil), the Au@CNTs@Cu foil exhibits enhanced Coulombic efficiency and better cycling stability. In the full-cell configuration, the Au@CNTs@Cu foil with predeposited Li shows superior stability and rate performance. This work provides a facial strategy to directly construct a 3D skeleton on commercial Cu foils with lithiophilic building blocks for stable and practical Li metal anodes.
Carbon-encapsulated transition metal catalysts have caught the interest of researchers in the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) due to their distinctive architectures and highly tunable electronic structures. In this work, we synthesized N-doped carbon encapsulated with CoNi nanoalloy particles (CoNi@NC) as the electrocatalysts. The metal-organic skeleton ZIF-67 nanocubes were first synthesized, and then Ni2+ ions were inserted to generate CoNi-ZIF precursors by a simple ion-exchange route, which was followed by pyrolysis and with urea for the introduction of nitrogen (N) at a low temperature to synthesize CoNi@NC composites. The results reveal that ZIF-67 pyrolysis can dope more N atoms in the carbon skeleton and that the pyrolysis temperature influences the ORR and OER performances. The sample prepared by CoNi@NC pyrolysis at 650 °C has a high N content (9.70%) and a large specific surface area (167 m2 g-1), with a positive ORR onset potential (Eonset) of 0.89 V vs. RHE and half-wave potential (E1/2) of 0.81 V vs. RHE in 0.1 M KOH, and the overpotential of the OER measured in 1 M KOH was only 286 mV at 10 mA cm-2. The highly efficient bifunctional ORR/OER electrocatalysts synthesized by this method can offer some insights into the design and synthesis of complex metal-organic frameworks (MOFs) hybrid structures and their derivatives as functional materials in energy storage.
The primary challenge for efficient H2 evolution and hydrogen energy conversion is to develop highly active and stable catalysts with simple and reliable preparation processes. In this regard, we have designed and synthesized a porous carbon-supported low-Pt alloy catalyst (Pt3Co/Co@C composite) using ZIF-67 as a template. It showed uniformly dispersed Pt3Co/Co on the porous carbon layer due to the confinement effect of the porous carbon layer. Pt3Co/Co@C demonstrated excellent activity for the hydrogen evolution reaction in the full pH range, with an overpotential of 187 mV in 0.5 M H2SO4 to attain 100 mA/cm2 as well as long-term stability. It also displayed superior mass activity for the oxygen reduction reaction (ORR) at 0.85 V (vs RHE) compared to the commercial Pt/C. Furthermore, the Pt3Co/Co@C catalyst exclusively enabled a four-electron reaction process under ORR conditions without the competitive pathway to H2O2. The current work provides guidance for the design and facile synthesis of Pt-based catalysts with enhanced performance.
In perovskite solar cells, the halide vacancy defects on the perovskite film surface/interface will instigate charge recombination, leading to a decrease in cell performance. In this study, cadmium sulfide (CdS) has been introduced into the precursor solution to reduce the halide vacancy defects and improve the cell performance. The highest efficiency of the device reaches 21.62%. Density functional theory calculation reveals that the incorporated Cd2+ ions can partially replace Pb2+ ions, thus forming a strong Cd-I bond and effectively reducing iodide vacancy defects (VI); at the same time, the loss of the charge recombination is significantly reduced because VI is filled by S2- ions. Besides, the substitution of Cd2+ for Pb2+ could increase the generation of PbI2, which can further passivate the grain boundary. Therefore, the stability of the cells, together with the efficiency of the power conversion efficiencies (PCEs), is also improved, maintaining 87.5% of its initial PCEs after being irradiated over 410 h. This work provides a very effective strategy to passivate the surface/interface defects of perovskite films for more efficient and stable optoelectronic devices.
We computationally study the transition process of a chiral difluorobenzo[c]phenanthrene (DFBcPh) molecule within non-polar fullerene C(260) to explore the confinement effect. We find blue-shifts in the infrared and Raman spectra of the molecule inside the fullerene relative to those of isolated systems. Six types of spectrum features of the molecule appear in the 0-60 cm(-1) band. Interestingly, the energy barrier of the chiral transformation of the molecule is elevated by 15.88 kcal mol(-1) upon the confinement by the fullerene, indicating improvement in the stability of the enantiomers. The protection by C(260) lowers the highest occupied molecular orbital energy level and lifts the lowest unoccupied molecular orbital energy level of the chiral molecule such that the chiral molecule is further chemically stabilized. We concluded that the confinement environment has an impact at the nanoscale on the enantiomer transformation process of the chiral molecule.
Fullerenes/chemistry , Hydrocarbons, Fluorinated/chemistry , Phenanthrenes/chemistry , Quantum Theory
The significance of the molecular chirality of drugs has been widely recognized due to the thalidomide tragedy. Most of the new drugs reaching the market today are single enantiomers, rather than racemic mixtures. However, many optically pure drugs, including thalidomide, undergo enantiomerization in vivo, thus negating the single enantiomers' benefits or inducing unexpected effects. A detailed atomic level understanding of chiral conversion, which is still largely lacking, is thus critical for drug development. Herein, we use first-principle density function theory (DFT) to explore the mechanism of enantiomerization of thalidomide. We have identified the two most plausible interconversion pathways for isolated thalidomide: 1)â proton transfer from the chiral carbon center to an adjacent carbonyl oxygen atom, followed by isomerization and rotation of the glutarimide ring (before the proton hops back to the chiral carbon atom); and 2)â a pathway that is the same as "1", but with the isomerization of the glutarimide ring occurring ahead of the initial proton transfer reaction. There are two remarkable energy barriers, 73.29 and 23.59â kcal mol(-1), corresponding to the proton transfer and the rotation of the glutarimide ring, respectively. Furthermore, we found that water effectively catalyzes the interconversion by facilitating the proton transfer with the highest energy barrier falling to approximately 30â kcal mol(-1), which, to our knowledge, is the first time that this important role of water in chiral conversion has been demonstrated. Finally, we show that the hydroxide ion can further lower the enantiomerization energy barrier to approximately 24â kcal mol(-1) by facilitating proton abstraction, which agrees well with recent experimental data under basic conditions. Our current findings highlight the importance of water and hydroxide ions in the enantiomerization of thalidomide and also provide new insights into the mechanism of enantiomerization at an atomic level.
Hydroxides/chemistry , Thalidomide/chemistry , Water/chemistry , Catalysis , Molecular Conformation , Piperidones/chemistry , Quantum Theory , Stereoisomerism , Thermodynamics
The adsorption of six free radicals (FRs) respectively on a graphene fragment was studied using a density functional tight-binding method with the inclusion of an empirical dispersion term in total energy. The results indicate that the different interaction paths between the FRs and the graphene lead to different forms of physical (PA) or chemical adsorptions (CA). The CA appears only in the condition where some of the nonhydrogen atoms are closer to the graphene, with the deformation occurring in the latter. The charge transfer increases with the increase in adsorption energy in every FR-graphene system. Although the deformation in the graphene is negligible in all PA cases, the FR is closer to the graphene and the graphene deformation is clearer in all CA cases, with all atomic displacements being larger than 0.1 Å. Our findings are useful not only for FR scavenging but also for studying the interaction between general molecules and material surfaces.
