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Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni 4+ species in surface reconstructed (oxy)hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni 4+ species, which is energetically favored by the multistep evolution of Ni 2+ →Ni 3+ →Ni 4+ . The dynamically constructed Ni 4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A g metal −1 and 0.483 s −1 at an overpotential of 300 mV in alkaline electrolyte, respectively. Electrocatalytic water oxidation is facilitated by high valence states, but these are challenging to achieve at low applied potentials. Here, authors report a multicomponent FeCoCrNi alloy with dynamically formed Ni 4+ species to offer high catalytic activity via lattice oxygen activation mechanism.

Lithium-sulfur batteries show great potential to achieve high-energy-density storage, but their long-term stability is still limited due to the shuttle effect caused by the dissolution of polysulfides into electrolyte. Herein, we report a strategy of significantly improving the polysulfides adsorption capability of cobaltous oxide by amorphization-induced surface electronic states modulation. The amorphous cobaltous oxide nanosheets as the cathode additives for lithium-sulfur batteries demonstrates the rate capability and cycling stability with an initial capacity of 1248.2 mAh g -1 at 1 C and a substantial capacity retention of 1037.3 mAh g -1 after 500 cycles. X-ray absorption spectroscopy analysis reveal that the coordination structures and symmetry of ligand field around Co atoms of cobaltous oxide nanosheets are notably changed after amorphization. Moreover, DFT studies further indicate that amorphization-induced re-distribution of d orbital makes more electrons occupy high energy level, thereby resulting in a high binding energy with polysulfides for favorable adsorption. Regulating the adsorption behaviour of the polysulfide species is the key to achieving highly stable Li-S batteries. Here, the authors show that amorphization-induced redistribution of d orbitals enable CoO to be a favourable candidate for polysulfide adsorption and conversion.

Smart membranes with responsive wettability show promise for controllably separating oil/water mixtures, including immiscible oil-water mixtures and surfactant-stabilized oil/water emulsions. However, the membranes are challenged by unsatisfactory external stimuli, inadequate wettability responsiveness, difficulty in scalability and poor self-cleaning performance. Here, we develop a capillary force-driven confinement self-assembling strategy to construct a scalable and stable CO 2 -responsive membrane for the smart separation of various oil/water systems. In this process, the CO 2 -responsive copolymer can homogeneously adhere to the membrane surface by manipulating the capillary force, generating a membrane with a large area up to 3600 cm 2 and excellent switching wettability between high hydrophobicity/underwater superoleophilicity and superhydrophilicity/underwater superoleophobicity under CO 2 /N 2 stimulation. The membrane can be applied to various oil/water systems, including immiscible mixtures, surfactant-stabilized emulsions, multiphase emulsions and pollutant-containing emulsions, demonstrating high separation efficiency (>99.9%), recyclability, and self-cleaning performance. Due to robust separation properties coupled with the excellent scalability, the membrane shows great implications for smart liquid separation. Smart membranes with responsive wettability show promise for controllably separating oil/water mixtures but it remains challenging to fabricate responsive and stable scalable membranes. Here, the authors develop a capillary force-driven self-assembling strategy to construct a scalable and stable CO2-responsive membrane for the smart separation of various oil/water systems.

Size engineering is deemed to be an adoptable method to boost the electrochemical properties of potassium‐ion storage; however, it remains a critical challenge to significantly reduce the nanoparticle size without compromising the uniformity. In this work, a series of MoP nanoparticle splotched nitrogen‐doped carbon nanosheets (MoP@NC) is synthesized. Due to the coordinate and hydrogen bonds in the water‐soluble polyacrylamide hydrogel, MoP is uniformly confined in a 3D porous NC to form ultrafine nanoparticles which facilitate the extreme exposure of abundant three‐phase boundaries (MoP, NC, and electrolyte) for ionic binding and storage. Consequently, MoP@NC‐1 delivers an excellent capacity performance (256.1 mAh g−1 at 0.1 A g−1) and long‐term cycling durability (89.9% capacitance retention after 800 cycles). It is further confirmed via density functional theory calculations that the smaller the MoP nanoparticle, the larger the three‐phase boundary achieved for favoring competitive binding energy toward potassium ions. Finally, MoP@NC‐1 is applied as highly electroactive additive for 3D printing ink to fabricate 3D‐printed potassium‐ion hybrid capacitors, which delivers high gravimetric energy/power density of 69.7 Wh kg−1/2041.6 W kg−1, as well as favorable areal energy/power density of 0.34 mWh cm−2/9.97 mW cm−2. Due to the usage of water‐soluble polyacrylamide as molecular skeleton and the strong chemical bond connection inside the hydrogel network, ultrafine MoP nanoparticles can be formed and evenly confined in 3D porous nitrogen‐doped carbon (NC) framework. This can create abundant three‐phase boundaries for efficient response between MoP, NC, and electrolyte, endowing high energy/power 3D‐printed potassium‐ion hybrid capacitors.

Lithium metal batteries (LMBs) have aroused extensive interest in the field of energy storage owing to the ultrahigh anode capacity. However, strong solvation of Li+ and slow interfacial ion transfer associated with conventional electrolytes limit their long‐cycle and high‐rate capabilities. Herein an electrolyte system based on fluoroalkyl ether 2,2,2‐trifluoroethyl‐1,1,2,3,3,3‐hexafluoropropyl ether (THE) and ether electrolytes is designed to effectively upgrade the long‐cycle and high‐rate performances of LMBs. THE owns large adsorption energy with ether‐based solvents, thus reducing Li+ interaction and solvation in ether electrolytes. With THE rich in fluoroalkyl groups adjacent to oxygen atoms, the electrolyte owns ultrahigh polarity, enabling solvation‐free Li+ transfer with a substantially decreased energy barrier and ten times enhancement in Li+ transference at the electrolyte/anode interface. In addition, the uniform adsorption of fluorine‐rich THE on the anode and subsequent LiF formation suppress dendrite formation and stabilize the solid electrolyte interphase layer. With the electrolyte, the lithium metal battery with a LiFePO4 cathode delivers unprecedented cyclic performances with only 0.0012% capacity loss per cycle over 5000 cycles at 10 C. Such enhancement is consistently observed for LMBs with other mainstream electrodes including LiCoO2 and LiNi0.5Mn0.3Co0.2O2, suggesting the generality of the electrolyte design for battery applications. This work designs an electrolyte system based on fluoroalkyl ether 2,2,2‐trifluoroethyl‐1,1,2,3,3,3‐hexafluoropropyl ether (THE) to effectively upgrade the long‐cycle and high‐rate performances of lithium metal batteries. With THE rich in fluoroalkyl groups adjacent to oxygen atoms, the electrolyte owns ultrahigh polarity and enables solvation‐free Li+ transfer with a substantially decreased energy barrier.

Constructing nitrogen (N2) adsorption and activation sites on semiconductors is the key to achieving efficient N2 photofixation. Herein, Mn–W dual‐metal sites on WO3 are designed toward efficient N2 photoreduction via controlled Mn doping. Impressively, the optimal 2.3% Mn‐doped WO3 (Mn‐WO3) exhibits a remarkable ammonia (NH3) production rate of 425 µmol gcat.−1 h−1, representing the best catalytic performance among the ever‐reported tungsten oxide‐based photocatalysts for N2 fixation. Quasi in situ synchrotron radiation X‐ray spectroscopy directly identifies that the Mn–W dual‐metal sites can enhance the polarization of the adsorbed N2, which is beneficial to the N2 activation. Further theoretical calculations reveal that the increased polarization is originated from the electron back‐donation into the antibonding orbitals of the adsorbed N2, hence lowering the reaction energy barrier toward the N2 photofixation. The concept of dual sites construction for inert molecule activation offers a powerful platform toward rational design of highly efficient catalysts for nitrogen fixation and beyond. The optimal 2.3% Mn‐doped WO3 exhibits an impressive NH3 production rate of 425 µmol gcat.−1 h−1. Further quasi in situ synchrotron radiation X‐ray spectroscopy and theoretical calculations reveal that the Mn–W dual‐metal sites can enhance the polarization of the adsorbed N2, hence lowering the reaction energy barrier toward the N2 photofixation.

The high unoccupied d band energy of Ni 3 N basically results in weak orbital coupling with water molecule, consequently leading to slow water dissociation kinetics. Herein, we demonstrate Cr doping can downshift the unoccupied d orbitals and strengthen the interfacial orbital coupling to boost the water dissociation kinetics. The prepared Cr-Ni 3 N/Ni displays an impressive overpotential of 37 mV at 10 mA·cm geo −2 , close to the benchmark Pt/C in 1.0 M KOH solution. Refined structural analysis reveals the Cr dopant exists as the Cr-N 6 states and the average d band energy of Ni 3 N is also lowered. Density functional theory calculation further confirms the downshifted d band energy can strengthen the orbital coupling between the unpaired electrons in O 2p and the unoccupied state of Ni 3d, which thus facilitates the water adsorption and dissociation. The work provides a new concept to achieve on-demand functions for hydrogen evolution catalysis and beyond, by regulating the interfacial orbital coupling.

Large cations such as potassium ion (K+) and sodium ion (Na+) could be introduced into the lithium-ion (Li-ion) battery system during material synthesis or battery assembly. However, the effect of these cations on charge storage or electrochemical performance has not been fully understood. In this study, sodium ion was taken as an example and introduced into the lithium titanium oxide (LTO) anode through the carboxymethyl cellulose (CMC) binder. After the charge/discharge cycles, these ions doped into the LTO lattice and improved both the lithium-ion diffusivity and the electronic conductivity of the anode. The sodium ion’s high concentration (>12.9%), however, resulted in internal doping of Na+ into the LTO lattice, which retarded the transfer of lithium ions due to repulsion and physical blocking. The systematic study presented here shows that large cations with an appropriate concentration in the electrode would be beneficial to the electrochemical performance of the Li-ion battery.

Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural (HMF) to the higher value-added 2,5-furandicarboxylic acid (FDCA). However, these catalysts still suffer from unsatisfactory activity and poor selectivity. A series of N-doped carbon-supported Co-based dual-metal nanoparticles (NPs) have been designed, among which the Co-Cu 1.4 -CN x exhibits enhanced HMF oxidative activity, achieving FDCA formation rates 4 times higher than that of pristine Co-CN x , with 100% FDCA selectivity. Density functional theory (DFT) calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the d-band center of Co-Cu 1.4 -CN x , thus reducing the energy barriers for the conversion of HMF to FDCA. Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.

Shrinking the size of a bulk metal into nanoscale leads to the discreteness of electronic energy levels, the so-called Kubo gap δ. Renormalization of the electronic properties with a tunable and size-dependent δ renders fascinating photon emission and electron tunneling. In contrast with usual three-dimensional (3D) metal clusters, here we demonstrate that Kubo gap δ can be achieved with a two-dimensional (2D) metallic transition metal dichalcogenide (i.e., 1T′-phase MoTe₂) nanocluster embedded in a semiconducting polymorph (i.e., 1H-phase MoTe₂). Such a 1T′/1H MoTe₂ nanodomain resembles a 3D metallic droplet squeezed in a 2D space which shows a strong polarization catastrophe while simultaneously maintaining its bond integrity, which is absent in traditional δ-gapped 3D clusters. The weak screening of the host 2D MoTe₂ leads to photon emission of such pseudometallic systems and a ballistic injection of carriers in the 1T′/1H/1T′ homojunctions which may find applications in sensors and 2D reconfigurable devices.