Electrochemical Oxidation of Nitrogen towards Direct Nitrate Production on Spinel Oxides

Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high‐temperature‐high‐pressure multi‐step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFe_xCo_2?xO₄ spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N?O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH^? for the generation of the second and third N?O bonds. Owing to the concerted catalysis, the ZnFe_0.4Co_1.6O₄ oxide demonstrates the highest nitrate production rate of 130±12 μmol h^?1 g_MO^?1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE).     

Antibiotics Separation with MXene Membranes Based on Regularly Stacked High‐Aspect‐Ratio Nanosheets

The uncontrolled release of antibiotics and pharmaceuticals into the environment is a worldwide increasing problem. Thus, highly efficient treatment technologies for wastewater are urgently needed. In this work, seven kinds of typical antibiotics (including water and alcohol soluble ones) are successfully separated from the corresponding aqueous and ethanolic solutions using highly regular laminated membranes. Our membranes are assembled with 2–4 μm titanium carbide nanosheets. The solvent permeance through such titanium carbide membrane is one order of magnitude higher than that through most polymeric nanofiltration membranes with similar antibiotics rejection. This high flux is due to the regular two‐dimensional (2D) structure resulting from the large aspect ratio of titanium carbide nanosheets. Moreover, the electrostatic interaction between the surface terminations and the antibiotics also affects the rejection and enhances the antifouling property. Such 2D titanium carbide membranes further broaden the application scope of laminated materials for separation and purification of high value added drugs in academia and industry.     

Towards Long‐Term Photostability of Nickel Hydroxide/BiVO4 Photoanodes for Oxygen Evolution Catalysts via In Situ Catalyst Tuning

Increasing long‐term photostability of BiVO₄ photoelectrode is an important issue for solar water splitting. The NiOOH oxygen evolution catalyst (OEC) has fast water oxidation kinetics compared to the FeOOH OEC. However, it generally shows a lower photoresponse and poor stability because of the more substantial interface recombination at the NiOOH/BiVO₄ junction. Herein, we utilize a plasma etching approach to reduce both interface/surface recombination at NiOOH/BiVO₄ and NiOOH/electrolyte junctions. Further, adding Fe²⁺ into the borate buffer electrolyte alleviates the active but unstable character of etched‐NiOOH/BiVO₄, leading to an outstanding oxygen evolution over 200 h. The improved charge transfer and photostability can be attributed to the active defects and a mixture of NiOOH/NiO/Ni in OEC induced by plasma etching. Metallic Ni acts as the ion source for the in situ generation of the NiFe OEC over long‐term durability.     

Rationally Designed Three‐Layered Cu2S@Carbon@MoS2 Hierarchical Nanoboxes for Efficient Sodium Storage

Hybrid materials, integrating the merits of individual components, are ideal structures for efficient sodium storage. However, the construction of hybrid structures with decent physical/electrochemical properties is still challenging. Now, the elaborate design and synthesis of hierarchical nanoboxes composed of three‐layered Cu₂S@carbon@MoS₂ as anode materials for sodium‐ion batteries is reported. Through a facile multistep template‐engaged strategy, ultrathin MoS₂ nanosheets are grown on nitrogen‐doped carbon‐coated Cu₂S nanoboxes to realize the Cu₂S@carbon@MoS₂ configuration. The design shortens the diffusion path of electrons/Na⁺ ions, accommodates the volume change of electrodes during cycling, enhances the electric conductivity of the hybrids, and offers abundant active sites for sodium uptake. By virtue of these advantages, these three‐layered Cu₂S@carbon@MoS₂ hierarchical nanoboxes show excellent electrochemical properties in terms of decent rate capability and stable cycle life.     

Regulating Charge Transfer of Lattice Oxygen in Single‐Atom‐Doped Titania for Hydrogen Evolution

Single‐atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single‐atom‐doped titania enables tunable hydrogen evolution reaction (HER) activity. First‐principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping‐induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single‐atom‐doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.     

Bridge Bonded Oxygen Ligands between Approximated FeN4 Sites Confer Catalysts with High ORR Performance

The applications of the most promising Fe—N–C catalysts are prohibited by their limited intrinsic activities. Manipulating the Fe energy level through anchoring electron‐withdrawing ligands is found effective in boosting the catalytic performance. However, such regulation remains elusive as the ligands are only uncontrollably introduced oweing to their energetically unstable nature. Herein, we report a rational manipulation strategy for introducing axial bonded O to the Fe sites, attained through hexa‐coordinating Fe with oxygen functional groups in the precursor. Moreover, the O modifier is stabilized by forming the Fe?O?Fe bridge bond, with the approximation of two FeN₄ sites. The energy level modulation thus created confers the sites with an intrinsic activity that is over 10 times higher than that of the normal FeN₄ site. Our finding opens a novel strategy to manage coordination environments at an atomic level for high activity ORR catalysts.     

Metal–Organic Framework Membrane Nanopores as Biomimetic Photoresponsive Ion Channels and Photodriven Ion Pumps

Biological ion channels and ion pumps with sub‐nanometer sizes modulate ion transport in response to external stimuli. Realizing such functions with sub‐nanometer solid‐state nanopores has been an important topic with wide practical applications. Herein, we demonstrate a biomimetic photoresponsive ion channel and photodriven ion pump using a porphyrin‐based metal–organic framework membrane with pore sizes comparable to hydrated ions. We show that the molecular‐size pores enable precise and robust optoelectronic ion transport modulation in a broad range of concentrations, unparalleled with conventional solid‐state nanopores. Upon decoration with platinum nanoparticles to form a Schottky barrier photodiode, photovoltage across the membrane is generated with “uphill” ion transport from low concentration to high concentration. These results may spark applications in energy conversion, ion sieving, and artificial photosynthesis.     

High‐Tc Enantiomeric Ferroelectrics Based on Homochiral Dabco‐derivatives (Dabco=1,4‐Diazabicyclo[2.2.2]octane)

1,4‐Diazabicyclo[2.2.2]octane (dabco) and its derivatives have been extensively utilized as building units of excellent molecular ferroelectrics for decades. However, the homochiral dabco‐based ferroelectric remains a blank. Herein, by adding a methyl (Me) group accompanied by the introduction of homochirality to the [H₂dabco]²⁺ in the non‐ferroelectric [H₂dabco][TFSA]₂ (TFSA=bis(trifluoromethylsulfonyl)ammonium), we successfully designed enantiomeric ferroelectrics [R and S‐2‐Me‐H₂dabco][TFSA]₂. The two enantiomers show two sequential phase transitions with transition temperature (T_c) as high as 405.8 K and 415.8 K, which is outstanding in both dabco‐based ferroelectrics and homochiral ferroelectrics. To our knowledge, [R and S‐2‐Me‐H₂dabco][TFSA]₂ are the first examples of dabco‐based homochiral ferroelectrics. This finding opens an avenue to construct dabco‐based homochiral ferroelectrics and will inspire the exploration of more eminent enantiomeric molecular ferroelectrics.