Element-dependent effects of alkali cations on nitrate reduction to ammonia.

Catalytic conversion of nitrate (NO3-) pollutants into ammonia (NH3) offers a sustainable and promising route for both wastewater treatment and NH3 synthesis. Alkali cations are prevalent in nitrate solutions, but their roles beyond charge balance in catalytic NO3- conversion have been generally ignored. Herein, we report the promotion effect of K+ cations in KNO3 solution for NO3- reduction over a TiO2-supported Ni single-atom catalyst (Ni1/TiO2). For photocatalytic NO3- reduction reaction, Ni1/TiO2 exhibited a 1.9-fold NH3 yield rate with nearly 100% selectivity in KNO3 solution relative to that in NaNO3 solution. Mechanistic studies reveal that the K+ cations from KNO3 gradually bonded with the surface of Ni1/TiO2, in situ forming a K-O-Ni moiety during reaction, whereas the Na+ ions were unable to interact with the catalyst in NaNO3 solution. The charge accumulation on the Ni sites induced by the incorporation of K atom promoted the adsorption and activation of NO3-. Furthermore, the K-O-Ni moiety facilitated the multiple proton-electron coupling of NO3- into NH3 by stabilizing the intermediates.

Engineering Dual CO2- and Photothermal-Responsive Membranes for Switchable Double Emulsion Separation.

Stimulus-responsive membranes demonstrate promising applications in switchable oil/water emulsion separations. However, they are unsuitable for the treatment of double emulsions like oil-in-water-in-oil (O/W/O) and water-in-oil-in-water (W/O/W) emulsions. For efficient separation of these complicated emulsions, fine control over the wettability, response time, and aperture structure of the membrane is required. Herein, dual-coated fibers consisting of primary photothermal-responsive and secondary CO2-responsive coatings are prepared by two steps. Automated weaving of these fibers produces membranes with photothermal- and CO2-responsive characteristics and narrow pore size distributions. These membranes exhibit fast switching wettability between superhydrophilicity (under CO2 stimulation) and high hydrophobicity (under near-infrared stimulation), achieving on-demand separation of various O/W/O and W/O/W emulsions with separation efficiencies exceeding 99.6%. Two-dimensional low-field nuclear magnetic resonance and correlated spectra technique are used to clarify the underlying mechanism of switchable double emulsion separation. The approach can effectively address the challenges associated with the use of stimulus-responsive membranes for double emulsion separation and facilitate the industrial application of these membranes.

Simultaneously Geometrical and Electronic Modulation of L10-PtZn by Trace Ge Boosts High-performance Oxygen Reduction Reaction.

Developing a highly active, durable, and low-platinum-based electrocatalyst for the cathodic oxygen reduction reaction (ORR) is for breaking the bottleneck of large-scale applications of proton exchange membrane fuel cells (PEMFCs). Herein, ultrafine PtZn intermetallic nanoparticles with low Pt-loading and trace germanium (Ge) involvement confined in the nitrogen-doped porous carbon (Ge-L10-PtZn@N-C) are reported. The Ge-L10-PtZn@N-C exhibit superior ORR activity with a mass activity of 3.04 A mg-1 Pt and specific activity of 4.69 mA cm-2, ≈12.2- and 10.2-times improvement compared to the commercial Pt/C (20%) at 0.90 V in 0.1 m KOH. The cathodic catalyst Ge-L10-PtZn@N-C assembled in the PEMFC shows encouraging peak power densities of 316.5 (at 0.86 V) and 417.2 mW cm-2 (at 0.91 V) in alkaline and acidic fuel-cell, respectively. The combination of experiment and density functional theory calculations (DFT) results robustly reveal that the participation of trace Ge can not only trigger a "growth site locking effect" to effectively inhibit nanoparticle growth, bring miniature nanoparticles, enhance dispersion uniformity, and achieve the exposure of the more electrochemical active site, but also effectively modulates the electronic structure, hence optimizing the adsorption/desorption of the oxygen intermediates.

Microstructure optimization of bioderived polyester nanofilms for antibiotic desalination via nanofiltration.

The successful implementation of thin-film composite membranes (TFCM) for challenging solute-solute separations in the pharmaceutical industry requires a fine control over the microstructure (size, distribution, and connectivity of the free-volume elements) and thickness of the selective layer. For example, desalinating antibiotic streams requires highly interconnected free-volume elements of the right size to block antibiotics but allow the passage of salt ions and water. Here, we introduce stevioside, a plant-derived contorted glycoside, as a promising aqueous phase monomer for optimizing the microstructure of TFCM made via interfacial polymerization. The low diffusion rate and moderate reactivity of stevioside, together with its nonplanar and distorted conformation, produced thin selective layers with an ideal microporosity for antibiotic desalination. For example, an optimized 18-nm membrane exhibited an unprecedented combination of high water permeance (81.2 liter m-2 hour-1 bar-1), antibiotic desalination efficiency (NaCl/tetracycline separation factor of 11.4), antifouling performance, and chlorine resistance.

Promoting CO2 Dynamic Activation via Micro-Engineering Technology for Enhancing Electrochemical CO2 Reduction.

Optimizing the coordination structure and microscopic reaction environment of isolated metal sites is promising for boosting catalytic activity for electrocatalytic CO2 reduction reaction (CO2 RR) but is still challenging to achieve. Herein, a newly electrostatic induced self-assembly strategy for encapsulating isolated Ni-C3 N1 moiety into hollow nano-reactor as I-Ni SA/NHCRs is developed, which achieves FECO  of 94.91% at -0.80 V, the CO partial current density of ≈-15.35 mA cm-2 , superior to that with outer Ni-C2 N2 moiety (94.47%, ≈-12.06 mA cm-2 ), or without hollow structure (92.30%, ≈-5.39 mA cm-2 ), and high FECO of ≈98.41% at 100 mA cm-2 in flow cell. COMSOL multiphysics finite-element method and density functional theory (DFT) calculation illustrate that the excellent activity for I-Ni SA/NHCRs should be attributed to the structure-enhanced kinetics process caused by its hollow nano-reactor structure and unique Ni-C3 N1 moiety, which can enrich electron on Ni sites and positively shift d-band center to the Fermi level to accelerate the adsorption and activation of CO2 molecule and *COOH formation. Meanwhile, this strategy also successfully steers the design of encapsulating isolated iron and cobalt sites into nano-reactor, while I-Ni SA/NHCRs-based zinc-CO2 battery assembled with a peak power density of 2.54 mW cm--2 is achieved.

Scalable and switchable CO2-responsive membranes with high wettability for separation of various oil/water systems.

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 CO2-responsive membrane for the smart separation of various oil/water systems. In this process, the CO2-responsive copolymer can homogeneously adhere to the membrane surface by manipulating the capillary force, generating a membrane with a large area up to 3600 cm2 and excellent switching wettability between high hydrophobicity/underwater superoleophilicity and superhydrophilicity/underwater superoleophobicity under CO2/N2 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.

Monitoring Electron Flow in Nickel Single-Atom Catalysts during Nitrogen Photofixation.

An efficient catalytic system for nitrogen (N2) photofixation generally consists of light-harvesting units, active sites, and an electron-transfer bridge. In order to track photogenerated electron flow between different functional units, it is highly desired to develop in situ characterization techniques with element-specific capability, surface sensitivity, and detection of unoccupied states. In this work, we developed in situ synchrotron radiation soft X-ray absorption spectroscopy (in situ sXAS) to probe the variation of electronic structure for a reaction system during N2 photoreduction. Nickel single-atom and ceria nanoparticle comodified reduced graphene oxide (CeO2/Ni-G) was designed as a model catalyst. In situ sXAS directly reveals the dynamic interfacial charge transfer of photogenerated electrons under illumination and the consequent charge accumulation at the catalytic active sites for N2 activation. This work provides a powerful tool to monitor the electronic structure evolution of active sites under reaction conditions for photocatalysis and beyond.

In situ Observation of Structural Evolution and Phase Engineering of Amorphous Materials during Crystal Nucleation.

The nucleation pathway determines the structures and thus properties of formed nanomaterials, which is governed by the free energy of the intermediate phase during nucleation. The amorphous structure, as one of the intermediate phases during nucleation, plays an important role in modulating the nucleation pathway. However, the process and mechanism of crystal nucleation from amorphous structures still need to be fully investigated. Here, in situ aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is employed to conduct real-time imaging of the nucleation of ultrathin amorphous nanosheets (NSs). The results indicate that their nucleation contains three distinct stages, i.e., aggregation of atoms, crystallization to form lattice-expanded nanocrystals, and relaxation of the lattice-expanded nanocrystals to form final nanocrystals. In particular, the crystallization processes of various amorphous materials are investigated systematically to form corresponding nanocrystals with unconventional crystalline phases, including face-centered-cubic (fcc) Ru, hexagonal-close-packed (hcp) Rh, and a new intermetallic IrCo alloy. In situ electron energy-loss spectroscopy (EELS) analysis unveils that the doped carbon in the original amorphous NSs can migrate to the surface during the nucleation process, stabilizing the obtained unconventional crystal phases transformed from the amorphous structures, which is also proven by density functional theory (DFT) calculations.

Zn0.52 V2 O5-a ⋠1.8 H2 O Cathode Stabilized by In Situ Phase Transformation for Aqueous Zinc-Ion Batteries with Ultra-Long Cyclability.

Developing cathode materials integrating good rate performance and sufficient cycle life is the key to commercialization of aqueous zinc-ion batteries. The hyperstable Zn0.52 V2 O5-a ⋅1.8 H2 O (ZVOH) cathode with excellent rate performance has been successfully developed via an in situ self-transformation from zinc-rich Zn3 V3 O8 (ZVO) in this study. Different from the common synthetic method of additional Zn2+ pre-insertion, ZVOH is obtained from the insertion of structural H2 O and the removal of excess Zn2+ in ZVO, ensuring the lattice structure of ZVOH remains relatively intact during the phase transition and rendering good structural stabilities. The ZVOH delivers a reversible capacity of 286.2 mAh g-1 at 0.2 A g-1 and of 161.5 mAh g-1 at 20 A g-1 over 18 000 cycles with a retention of 95.4 %, demonstrating excellent rate performance and cyclic stability. We also provide new insights on the structural self-optimization of Znx (CF3 SO3 )y (OH)2x-y ⋅n H2 O byproducts and the effect on the mobility of Zn2+ by theoretical calculations and experimental evidence.

Reversing the Nucleophilicity of Active Sites in CoP2 Enables Exceptional Hydrogen Evolution Catalysis.

Precisely constructing the local configurations of active sites to achieve on-demand catalytic functions is highly critical yet challenging. Herein, an anion-deficient strategy to precisely capture Ru single atoms on the anion vacancies of CoP2 (Ru-SA/Pv-CoP2 ) is developed. Refined structural characterizations reveal that the Ru single atoms preferably bind to the anion vacancy sites and consequently build a superior catalytic surface with neighboring CoP and CoRu coordination states for the hydrogen evolution reaction (HER) catalysis. The prepared Ru-SA/Pv-CoP2 nanowires exhibit an unprecedented overpotential of 17 mV at 10 mA cm-2geo , and the corresponding mass activity is 52.2 times higher than the benchmark Pt/C catalyst at the overpotential of 50 mV. Theoretical analysis illustrates that the introduced Ru-SAs can reverse electrons state distribution (from nucleophilic P sites to electrophilic Ru sites) and boost the activation of water molecules and hydrogen production. More importantly, such a construction strategy is also applicable for Pt single atom coupling, suggesting its generality in building catalytic sites. The capability to precisely construct active sites offers a powerful platform to manipulate the catalytic performance of HER catalysts and beyond.

High-Polarity Fluoroalkyl Ether Electrolyte Enables Solvation-Free Li+ Transfer for High-Rate Lithium Metal Batteries.

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 LiNi0.5 Mn0.3 Co0.2 O2 , suggesting the generality of the electrolyte design for battery applications.

Amorphization-induced surface electronic states modulation of cobaltous oxide nanosheets for lithium-sulfur batteries.

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.

Prototypical Study of Double-Layered Cathodes for Aqueous Rechargeable Static Zn-I2 Batteries.

Aqueous rechargeable zinc-iodine batteries (ZIBs) are promising candidates for grid energy storage because they are safe and low-cost and have high energy density. However, the shuttling of highly soluble triiodide ions severely limits the device's Coulombic efficiency. Herein, we demonstrate for the first time a double-layered cathode configuration with a conductive layer (CL) coupled with an adsorptive layer (AL) for ZIBs. This unique cathode structure enables the formation and reduction of adsorbed I3- ions at the CL/AL interface, successfully suppressing triiodide ion shuttling. A prototypical ZIB using a carbon cloth as the CL and a polypyrrole layer as the AL simultaneously achieves outstanding Coulombic efficiency (up to 95.6%) and voltage efficiency (up to 91.3%) in the aqueous ZnI2 electrolyte even at high-rate intermittent charging/discharging, without the need of ion selective membranes. These findings provide new insights to the design and fabrication of ZIBs and other batteries based on conversion reactions.

Ultrafine MoP Nanoparticle Splotched Nitrogen-Doped Carbon Nanosheets Enabling High-Performance 3D-Printed Potassium-Ion Hybrid Capacitors.

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.

Spatially Confined Formation of Single Atoms in Highly Porous Carbon Nitride Nanoreactors.

Reducing the size of a catalyst to a single atom (SA) level can dramatically change its physicochemical properties and significantly boost its catalytic activity. However, the massive synthesis of SA catalysts still remains a grand challenge mainly because of the aggregation and nucleation of the generated atoms during the reaction. Here, we design and implement a spatially confined synthetic strategy based on a porous-hollow carbon nitride (p-CN) coordinated with 1-butyl-3-methylimidazole hexafluorophosphate, which can act as a nanoreactor and allow us to obtain metal SA catalysts (p-CN@M SAs). This relatively easy and highly effective method provides a way to massively synthesize single/multiple atoms (p-CN@M SAs, M = Pt, Pd, Cu, Fe, etc.). Moreover, the amorphous NiB-coated p-CN@Pt SAs can further increase the loading amount of Pt SAs to 3.7 wt %. The synthesized p-CN@Pt&NiB electrocatalyst exhibits an extraordinary hydrogen evolution reaction activity with the overpotential of 40.6 mV@10 mA/cm-2 and the Tofel slope of 29.26 mV/dec.

Tailoring the d-Band Center of Double-Perovskite LaCoxNi1-xO3 Nanorods for High Activity in Artificial N2 Fixation.

The d-band center of a catalyst can be applied for the prediction of its catalytic activity, but the application of d-band theory for the electrocatalytic nitrogen reduction reaction (eNRR) has rarely been studied in perovskite materials. In this work, a series of double-perovskite LaCoxNi1-xO3 (LCNO) nanorods (NRs) were synthesized as models, where the d-band centers can be modulated by changing the stoichiometric ratios between Co and Ni elements. Experimentally, the LCNO-III NRs (x = 0.5) attained the highest faradic efficiency and NH3 yield rate among various LCNO NRs. This result matches well with the finding from theoretical calculations that LCNO-III has the most positive d-band center (εd = -0.96 eV vs Fermi level), thus confirming that LCNO-III shows the strongest adsorption ability for N2 molecules (adsorption energy value of -2.01 eV) for the subsequent N2 activation and reduction reactions. Therefore, this work proposes a general rule to adopt for developing novel catalysts (especially perovskite-based catalysts) for substantially increasing the eNRR activity by modulating the corresponding d-band centers.

Three-Phase Boundary in Cross-Coupled Micro-Mesoporous Networks Enabling 3D-Printed and Ionogel-Based Quasi-Solid-State Micro-Supercapacitors.

The construction of advanced micro-supercapacitors (MSCs) with both wide working-voltage and high energy density is promising but still challenging. In this work, a series of nitrogen-doped, cross-coupled micro-mesoporous carbon-metal networks (N-STC/Mx Oy ) is developed as robust additives to 3D printing inks for MSCs fabrication. Taking the N-STC/Fe2 O3 nanocomposite as an example, both experimental results and theoretical simulations reveal that the well-developed hierarchical networks with abundantly decorated ultrafine Fe2 O3 nanoparticles not only significantly facilitate the ion adsorption at its three-phase boundaries (Fe2 O3 , N-STC, and electrolyte), but also greatly favor ionic diffusion/transport with shortened pathways. Consequently, the as-prepared N-STC/Fe2 O3 electrode delivers a high gravimetric capacitance (267 F g-1 at 2 mV s-1 ) and outstanding stability in a liquid-electrolyte-based symmetric device, as well as a record-high energy density of 114 Wh kg-1 for an asymmetric supercapacitor. Particularly, the gravimetric capacitance of the ionogel-based quasi-solid-state MSCs by 3D printing reaches 377 F g-1 and the device can operate under a wide temperature range (-10 to 60 °C).

Lattice-Strain Engineering of Homogeneous NiS0.5 Se0.5 Core-Shell Nanostructure as a Highly Efficient and Robust Electrocatalyst for Overall Water Splitting.

Developing highly-efficient non-noble-metal electrocatalysts for water splitting is crucial for the development of clean and reversible hydrogen energy. Introducing lattice strain is an effective strategy to develop efficient electrocatalysts. However, lattice strain is typically co-created with heterostructure, vacancy, or substrate effects, which complicate the identification of the strain-activity correlation. Herein, a series of lattice-strained homogeneous NiSx Se1- x nanosheets@nanorods hybrids are designed and synthesized by a facile strategy. The NiS0.5 Se0.5 with ≈2.7% lattice strain exhibits outstanding activity for hydrogen and oxygen evolution reaction (HER/OER), affording low overpotentials of 70 and 257 mV at 10 mA cm-2 , respectively, as well as excellent long-term durability even at a large current density of 100 mA cm-2 (300 h), significantly superior to other benchmarks and the precious metal catalysts. Experimental and theoretical calculation results reveal that the generated lattice strain decreases the metal d-orbital overlap, leading to a narrower bandwidth and a closer d-band center toward the Fermi level. Thus, NiS0.5 Se0.5 possesses favorable H* adsorption kinetics for HER and lower energy barriers for OER. This work provides a new insight to regulate the lattice strain of advanced catalyst materials and further improve the performance of energy conversion technologies.

Synergistic Interface-Assisted Electrode-Electrolyte Coupling Toward Advanced Charge Storage.

Owing to the limited charge storage capability of transitional metal oxides in aqueous electrolytes, the use of redox electrolytes (RE) represents a promising strategy to further increase the energy density of aqueous batteries or pseudocapacitors. The usual coupling of an electrode and an RE possesses weak electrode/RE interaction and weak adsorption of redox moieties on the electrode, resulting in a low capacity contribution and fast self-discharge. In this work, Fe(CN)6 4- groups are grafted on the surface of Co3 O4 electrode via formation of CoN bonds, creating a synergistic interface between the electrode and the RE. With such an interface, the coupled Co3 O4 -RE system exhibits greatly enhanced charge storage from both Co3 O4 and RE, delivering a large reversible capacity of ≈1000 mC cm-2 together with greatly reduced self-discharge. The significantly improved electrochemical activity of Co3 O4 can be attributed to the tuned work function via charge injection from Fe(CN)6 4- , while the greatly enhanced adsorption of K3 Fe(CN)6 molecules is achieved by the interface induced dipole-dipole interaction on the liquid side. Furthermore, this enhanced electrode-electrolyte coupling is also applicable in the NiO-RE system, demonstrating that the synergistic interface design can be a general strategy to integrate electrode and electrolyte for high-performance energy storage devices.

Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation.

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 Ni4+ 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 Ni4+ species, which is energetically favored by the multistep evolution of Ni2+→Ni3+→Ni4+. The dynamically constructed Ni4+ 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 gmetal-1 and 0.483 s-1 at an overpotential of 300 mV in alkaline electrolyte, respectively.