"Polyoxometalate electron sponge" induces the accurate regulation of electron states at Ni sites to enhance oxidation of water.

Because of their special features, NiFe-LDHs (nickel iron layered double hydroxides) are prospective OER (oxygen evolution reaction) catalysts that might be utilized to catalyse the electrolysis of water and produce hydrogen to address the energy crisis. In this work, the electronic structure and electrocatalytic performance of the NiFe-LDH were accurately regulated by optimizing the Ni sites, which was enabled by adjacent metal sites coordinated with the "polyoxometalate electron sponge". With extension of the modification time, the Ni 2p binding energy, the Ni3+/Ni2+ ratio and the OER properties were gradually tuned, which indicated accurate regulation of active Ni sites by the "polyoxometalate electron sponge" on a temporal scale. Additionally, NiFe-LDH-PW12-12 h (NiFe-LDH modified by polyoxometalate anions for 12 h) showed the highest OER performance along with fast electron transfer, superior reaction kinetics and electrochemical durability, with an overpotential ∼68 mV lower than that of NiFe-LDH. This work provides an accurate strategy for regulating the electronic structures of active metal sites for the OER.

Highly Ordered Hierarchical Macro-Mesoporous Carbon-Supported Cobalt Electrocatalyst for Efficient Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) and their derivatives have been extensively employed in Oxygen Evolution Reaction (OER) catalysts due to their significantly larger specific surface areas, distinct metal centers, and well-organized porous structures. However, the microporous structure of MOFs and their derivatives presents mass transfer resistance, limiting their further development. Drawing inspiration from hierarchical structures allowing for the transport and exchange of substances in the biological world, we designed and fabricated biomimetic layered porous structures within ZIF-67 and its derivatives. Based on this, we achieved a three-dimensional ordered layered porous nitrogen-doped carbon-coated magnetic cobalt catalyst (3DOLP Co@NDC) with a biomimetic pore structure. It is found that the 3DOLP Co@NDC (352 mV @10 mA cm-1) was better than Co@NDC (391 mV @10 mA cm-1). The introduction of a three-dimensional ordered layered porous structure is conducive to increasing the specific surface area of the material, increasing the electrochemical active area, and improving the catalytic performance of the material. The introduction of a three-dimensional ordered layered porous structure would help to build a bionic grade pore structure. The existence of biomimetic grade pore structure can effectively reduce the mass transfer resistance, improve the material exchange efficiency, and accelerate the reaction kinetics.

Single-Atom Mn Catalysts via Integration with Mn Sub Nano-Clusters Synergistically Enhance Oxygen Reduction Reaction.

Integrating single atoms and clusters into one system represents a novel strategy for achieving the desired catalytic performance. In comparison to single-atom catalysts, catalysts combining single atoms and clusters harness the advantages of both, thus displaying greater potential. Nevertheless, constructing single-atom-cluster systems remains challenging, and the fundamental mechanism for enhancing catalytic activity remains elusive. In this study, a directly confined preparation of a 3D hollow sea urchin-like carbon structure (MnSA/MnAC-SSCNR) is developed. Mn single atoms synergistically interact with Mn clusters, optimizing and reducing energy barriers in the reaction pathway, thus enhancing reaction kinetics. Consequently, in contrast to Mn single-atom catalysts (MnSA-SSCNR), MnSA/MnAC-SSCNR exhibits significantly improved oxygen reduction activity, with a half-wave potential (E1/2) of 0.90 V in 0.1 m KOH, surpassing that of MnSA-SSCNR and Pt/C. This work demonstrates a strategy of remote synergy between heterogeneous single atoms and clusters, which not only contributes to electrocatalytic reactions but also holds potential for reactions involving more complex products.

Terephthalic Acid Intercalated CoNi-LDH Materials for Improved Li-O2 Battery.

CoNi-LDH (layered CoNi double hydroxides) hollow nanocages with specific morphology are obtained by Ni ion etching of ZIF-67 (Zeolitic imidazolate framework-67). The structure of the layered materials is further modified by molecular intercalation. The original interlayer anions are replaced by the ion exchange effect of terephthalic acid, which helps to increase the interlayer distance of the material. The intercalated cage-like structures not only benefit for the storage of oxygen, and the discharge product reaction, but also have more support between the material layers. The experimental results show that the excessive use of intercalation agent will affect structural stability of the intercalated CoNi-LDH. By adjusting the amount of terephthalic acid, the intercalated CoNi-LDH-2 (with 0.02 mmol terephthalic acid intercalated) is not easy to collapse after 209 cycles and shows the best electrochemical performance in Li-O2 battery.

Charge Transport Dynamics of Quasi-Type II Perovskite Janus Nanocrystals in High-Performance Photoconductors.

CsPbBr3-Pb4S3Br2 Janus nanocrystals (NCs) are the only nanomaterial where the epitaxial structure of perovskite and chalcogenide materials has been realized at the nanoscale, but their exciton dynamics mechanism has not yet been thoroughly investigated or applied in photodetection applications. This work reports an attractive device performance of perovskite photoconductors based on epitaxial CsPbBr3-Pb4S3Br2 Janus NCs, as well as the carrier relaxation and transfer mechanism of the heterojunction. By a combination of transient optical absorption and quantum dynamics simulation, it is demonstrated that the photogenerated holes on CsPbBr3 can be successfully extracted by Pb4S3Br2, while the hole transfer proceeds about three times faster than energy loss and remains "hot" for about 300 fs. This feature has favorable effects on long-range charge separation and transport; therefore, the Janus NCs photoconductors exhibit an exceptional responsivity of 34.0 A W-1 and specific detectivity of 1.26 × 1014 Jones.

Highly Efficient White Emission from Semiconductor Ink Based on Copper Iodide Nanoclusters.

Recent developments in the perovskite field have aimed at exploring cluster-based organic-inorganic copper(I) halides as novel luminescent materials because of their low toxicity and structural diversity. However, the poor framework stability and low dispersion in solvent constitute the key challenges to their practical applications such as luminescent inks. Herein, we report the preparation of highly luminescent inks via one-pot solution synthesis, which consisted of ionic CumIn clusters (tetrabutylammonium copper iodide) coupled with polymer polyvinylpyrrolidone (PVP). Benefiting from the high-affinity PVP to stabilize and disperse the Cu-I inorganic units, the obtained hybrid nanocrystals exhibit high structural stabilitiy/photostability and good dispersion in ethanol. The characteristics of bright white light emission from inks were explored by temperature-dependent photoluminescence experiments and theoretical calculations. Attractively, the stable, highly luminescent inks show great potential for practical applications, such as anticounterfeiting and imaging identification. Our study offers a new material designing strategy that may be generalized to many other material classes.

Ultrathin Two-Dimensional Bimetal-Organic Framework Nanosheets as High-Performance Electrocatalysts for Benzyl Alcohol Oxidation.

Ultrathin two-dimensional metal-organic frameworks (2D MOFs) have the potential to improve the oxidation of benzyl alcohol (BA) with a large surface area and open catalytic active sites. To achieve high-efficiency electrocatalysts for the oxidation of benzyl alcohol, a moderate solvothermal method was evolved to synthesize a series of 2D MOFs on nickel foam (Ni-MOF/NF, NiCo-61-MOF/NF, NiCo-21-MOF/NF). As the electrocatalyst used for the oxidation of benzyl alcohol, NiCo-61-MOF/NF presented a lower overpotential and superior chemical durability than other electrocatalysts; it only required a potential of ∼1.52 V (vs RHE) to reach 338.16 mA cm-2, with an oxidation efficiency of more than 86%. Besides, after continuous electrocatalysis for 20 000 s at 1.42 V (vs RHE), the current density of NiCo-61-MOF/NF nanosheets was still 38.67 mA cm-2 with 77.34% retention. This demonstrated that NiCo-61-MOF/NF nanosheet electrocatalysts had great potential for benzyl alcohol oxidation. From both the experimental and theoretical studies, it was discovered that NiCo-61-MOF/NF nanosheets have the highest electrocatalytic activity due to their distinctive ultrathin 2D structure, optimized electron structure, and more accessible active sites. This finding would pave a brand-new thought for the design of electrocatalysts with electrocatalytic activity for benzyl alcohol oxidation (EBO).

Crystal Phase Conversion on Cobalt Oxide: Stable Adsorption toward LiO2 for Film-Like Discharge Products Generation in Li-O2 Battery.

Regulating the structure and morphology of discharge product is one of the key points for developing high performance Li-O2 batteries (LOBs). In this study, the reaction mechanism of LOB is successfully controlled by the regulated fine structure of cobalt oxide through tuning the crystallization process. It is demonstrated that the cobalt oxide with lower crystallinity shows stronger affinity toward LiO2 , inducing the growth of film-like LiO2 on the electrode surface and inhibiting the further conversion to Li2 O2 . The batteries catalyzed by the lower crystallinity cobalt oxide hollow spheres which pyrolyzed from ZIF-67 at 260 °C (ZIF-67-260), go through the generation and decomposition of amorphous film-like LiO2 , which significantly reduces the charge overpotential and improves the cycle life. By contrast, the ZIF-67 hollow spheres pyrolyzed at 320 °C (ZIF-67-320) with better crystallinity are more likely to go through the solution-mediated mechanism and induce the aggregation of discharge product, resulting in the sluggish kinetics and limited performance. The combined density functional theory data also directly support the strong relationship between the adsorption toward LiO2 by the electrocatalyst and the battery performance. This work provides an important way for tuning the intermediate and constructing the high-performance battery system.

Regulating the Spin State of FeIII Enhances the Magnetic Effect of the Molecular Catalysis Mechanism.

Aqueous-phase oxygen evolution reaction (OER) is the bottleneck of water splitting. The formation of the O-O bond involves the generation of paramagnetic oxygen molecules from the diamagnetic hydroxides. The spin configurations might play an important role in aqueous-phase molecular electrocatalysis. However, spintronic electrocatalysis is almost an uncultivated land for the exploration of the oxygen molecular catalysis process. Herein, we present a novel magnetic FeIII site spin-splitting strategy, wherein the electronic structure and spin states of the FeIII sites are effectively induced and optimized by the Jahn-Teller effect of Cu2+. The theoretical calculations and operando attenuated total reflectance-infrared Fourier transform infrared (ATR FT-IR) reveal the facilitation for the O-O bond formation, which accelerates the production of O2 from OH- and improves the OER activity. The Cu1-Ni6Fe2-LDH catalyst exhibits a low overpotential of 210 mV at 10 mA cm-2 and a low Tafel slope (33.7 mV dec-1), better than those of the initial Cu0-Ni6Fe2-LDHs (278 mV, 101.6 mV dec-1). With the Cu2+ regulation, we have realized the transformation of NiFe-LDHs from ferrimagnets to ferromagnets and showcase that the OER performance of Cu-NiFe-LDHs significantly increases compared with that of NiFe-LDHs under the effect of a magnetic field for the first time. The magnetic-field-assisted Cu1-Ni6Fe2-LDHs provide an ultralow overpotential of 180 mV at 10 mA cm-2, which is currently one of the best OER performances. The combination of the magnetic field and spin configuration provides new principles for the development of high-performance catalysts and understandings of the catalytic mechanism from the spintronic level.

Theoretical Design and Structural Modulation of a Surface-Functionalized Ti3C2Tx MXene-Based Heterojunction Electrocatalyst for a Li-Oxygen Battery.

Two-dimensional MXene with high conductivity has metastable Ti atoms and inert functional groups on the surface, greatly limiting application in surface-related electrocatalytic reactions. A surface-functionalized nitrogen-doped two-dimensional TiO2/Ti3C2Tx heterojunction (N-TiO2/Ti3C2Tx) was fabricated theoretically, with high conductivity and optimized electrocatalytic active sites. Based on the conductive substrate of Ti3C2Tx, the heterojunction remained metallic and efficiently accelerated the transfer of Li+ and electrons in the electrode. More importantly, the precise regulation of active sites in the N-TiO2/Ti3C2Tx heterojunction optimized the adsorption for LiO2 and Li2O2, facilitating the sluggish kinetics with a lowest theoretical overpotential in both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Employed as an electrocatalyst in a Li-oxygen battery (Li-O2 battery), it demonstrated a high specific capacity of 15 298 mAh g-1 and a superior cyclability with more than 200 cycles at 500 mA g-1, as well as the swiftly reduced overpotential. Furthermore, combined with the in situ differential electrochemical mass spectrometry, ex situ Raman spectra, and SEM tests, the N-TiO2/Ti3C2Tx heterojunction electrode presented a superior stability and reduced side reaction along with the high performance toward the ORR and OER. It provides an efficient insight for the design of high-performance electrocatalysts for metal-oxygen batteries.

Tuning the oxygen vacancy of mixed multiple oxidation states nanowires for improving Li-air battery performance.

Mixed multiple oxidation states CoMoO4 nanowires (electrocatalysts) with tunable intrinsic oxygen vacancies were fabricated. CoMoO4 with proper oxygen vacancy can be employed to construct a Li-air battery with a high capacity and stable cyclability. This is possible because CoMoO4 contains surface oxygen vacancies, which result in the unit of CoMo bond, that is important for electrocatalysts used in Li-air batteries. Both the experimental and theoretical results demonstrate that the surface oxygen vacancies containing CoMoO4 nanowires have a higher electrocatalytic activity. This shows that the highly efficient electrocatalysts used for Li-air batteries were designed to modify the redox properties of the mixed metal oxide in the catalytic active sites. This successful material design led to an improved strategy for high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities based on the fast formation and extinction of ORR products.

Oxygen Vacancy-Rich RuO2-Co3O4 Nanohybrids as Improved Electrocatalysts for Li-O2 Batteries.

Lithium oxygen (Li-O2) batteries have shown great potential as new energy-storage devices due to the high theoretical energy density. However, there are still substantial problems to be solved before practical application, including large overpotential, low energy efficiency, and poor cycle life. Herein, we have successfully synthesized a RuO2-Co3O4 nanohybrid with a rich oxygen vacancy and large specific surface area. The Li-O2 batteries based on the RuO2-Co3O4 nanohybrid shown obviously reduced overpotential and improved circulatory property, which can cycle stably for more than 100 cycles at a current density of 200 mA g-1. Experimental results and density function theory calculation prove that the introduction of RuO2 can increase oxygen vacancy concentration of Co3O4 and accelerate the charge transfer. Meanwhile, the hollow and porous structure leads to a large specific surface area about 104.5 m2 g-1, exposing more active sites. Due to the synergistic effect, the catalyst of the RuO2-Co3O4 nanohybrid can significantly reduce the adsorption energy of the LiO2 intermediate, thereby reducing the overpotential effectively.

"Lewis Base-Hungry" Amorphous-Crystalline Nickel Borate-Nickel Sulfide Heterostructures by In Situ Structural Engineering as Effective Bifunctional Electrocatalysts toward Overall Water Splitting.

The development of high-performance, low-cost, and long-lasting electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is urgently needed for effective electrochemical water splitting. In the present study, an engineering process was employed to prepare "Lewis base-hungry" amorphous-crystalline nickel borate-nickel sulfide (Ni3(BO3)2-Ni3S2) heterostructures, which exhibited unprecedentedly high electrocatalytic activity toward both OER and HER in alkaline media. The optimal Ni3(BO3)2-Ni3S2/nickel foam (Ni3(BO3)2-Ni3S2/NF) electrode displayed an ultralow overpotential of only -92 and +217 mV to reach the current density of 10 mA cm-2 for HER and OER, respectively. When the Ni3(BO3)2-Ni3S2/NF electrode was used as both the anode and cathode for overall water splitting, a low cell voltage of 1.49 V was needed to achieve the current density of 10 mA cm-2, which was superior to the performance of most noble metal-free electrocatalysts. Results from density functional theory calculations showed that the Lewis base-hungry sites in the heterostructures effectively enhanced the chemisorption of hydrogen and oxygen intermediates, a critical step in HER and OER electrocatalysis. Results from this study highlight the significance of rational design and engineering of heterostructured materials for the development of high-efficiency electrocatalysts.

Engineering Lithium Ions Embedded in NiFe Layered Double Hydroxide Lattices To Activate Laminated Ni2+ Sites as High-Efficiency Oxygen Evolution Reaction Catalysts.

NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni2+ to the surroundings of Li+ , resulting in electron-deficient properties of the Ni sites, which would function as "electron-hungry" sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li-NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm-2 , which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO2 . Reasonable intercalation adjustment effectively activates laminated Ni2+ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials.

Polypyrrole-Mo3S13: An Efficient Sorbent for the Capture of Hg2+ and Highly Selective Extraction of Ag+ over Cu2.

The new material Polypyrrole-Mo3S13 (abbr. Mo3S13-Ppy) is a new material prepared by ion-exchange between Ppy-NO3 and (NH4)2Mo3S13. The Mo3S13-Ppy was designed to exhibit strong selectivity for Ag+ and highly toxic Hg2+ in mixtures with other ions. It displays an apparent selectivity ranking of Hg2+ > Ag+ ≥ Co2+, Ni2+, Cu2+, Zn2+, Cd2+, and Pb2+. The strong affinity of Mo3S13-Ppy for Ag+ and Hg2+ was confirmed with extremely high distribution coefficients (Kd) (∼107 mL/g) and remarkable removal efficiencies (>99.99%), resulting in <1 ppb concentrations of these ions. Furthermore, Mo3S13-Ppy achieved excellent separation selectivity for Ag+ from Cu2+ (even at a high Cu2+/Ag+ ratio, the molar ratio of 867 and mass ratio of 500) because of the special structure of Mo3S132- and its component Mo4+ and (S2)2-. This is promising for the direct extraction of low-grade silver from copper-rich minerals. The maximum Ag uptake capacity of 408 mg/g is redox-based and surprisingly involves the deposition of large, millimeter sized, metallic silver (Ag0) crystals on the surface of Mo3S13-Ppy.

The design of hollow PdO-Co3O4 nano-dodecahedrons with moderate catalytic activity for Li-O2 batteries.

Hollow PdO-Co3O4 nano-dodecahedrons with moderate catalytic activity were designed as electrocatalysts for Li-O2 batteries, and not only reduce the overpotentials effectively but also improve the reversibility of the ORR and OER, and cycle for more than 90 cycles stably with extremely low overpotentials.

Morphology-Controlled Synthesis of Ni-MOFs with Highly Enhanced Electrocatalytic Performance for Urea Oxidation.

MOFs present potential application in electrocatalysis. The structure-activity of the Ni-MOFs with different morphologies, nanowires, neurons, and urchins is systemically investigated. The Ni-MOFs were controllably synthesized via the facile solvothermal method. Among them, the Ni-MOF nanowires are endowed with the highest electrocatalytic activity due to the unique structure, more exposed active sites, lower charge transfer resistance, and the fast and direct electron transfer in 1D structures. The typical morphology of the Ni-MOF nanowires is ca. 10 nm in diameter and several micrometers in length. When employed as an electrocatalyst in urea oxidation reaction, it exhibits a lower overpotential than and superior stability to the Ni-MOFs with other morphologies. Ni-MOF nanowires require a potential of ∼0.80 V (vs Ag/AgCl) to obtain 160 mA cm-2. In addition, after continuous electrocatalyzing for 3600 s at 0.40 V (vs Ag/AgCl), the current density retention of Ni-MOF nanowires could still reach more than 60% (>12 mA cm-2), which demonstrates Ni-MOF nanowires as promising electrocatalysts for urea oxidation.

Needle grass-like cobalt hydrogen phosphate on Ni foam as an effective and stable electrocatalyst for the oxygen evolution reaction.

Exploring efficient non-precious metal electrocatalysts for the oxygen evolution reaction (OER) is a challenging task in sustainable energy systems. Herein, facile and novel three dimensional (3D) needle grass-like CoHPO4·H2O on Ni foam (CoHPO/NF) has been prepared as an effective and robust OER electrocatalyst for the first time. The unique 3D topological structure of CoHPO exposes more electrocatalytic active sites and facilitates mass transport. The coordinated HPO42- anions work as OH- traps to synergistically enhance the process of the OER. Because of these advantages, it exhibits an extraordinary OER performance with a low overpotential of only 350 mV at 50 mA cm-2. Notably, it also exhibits excellent long-term stability. According to the theoretical calculations, the electron structure of the Co was significantly influenced by the coupled HPO42- species, which leads to superior activity for the OER. All the findings imply that CoHPO/NF is a promising material to substitute for noble metals in overall water splitting.

Hierarchical Nanoassembly of MoS2/Co9S8/Ni3S2/Ni as a Highly Efficient Electrocatalyst for Overall Water Splitting in a Wide pH Range.

The design of low-cost yet high-efficiency electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) over a wide pH range is highly challenging. We now report a hierarchical co-assembly of interacting MoS2 and Co9S8 nanosheets attached on Ni3S2 nanorod arrays which are supported on nickel foam (NF). This tiered structure endows high performance toward HER and OER over a very broad pH range. By adjusting the molar ratio of the Co:Mo precursors, we have created CoMoNiS-NF- xy composites ( x: y means Co:Mo molar ratios ranging from 5:1 to 1:3) with controllable morphology and composition. The three-dimensional composites have an abundance of active sites capable of universal pH catalytic HER and OER activity. The CoMoNiS-NF-31 demonstrates the best electrocatalytic activity, giving ultralow overpotentials (113, 103, and 117 mV for HER and 166, 228, and 405 mV for OER) to achieve a current density of 10 mA cm-2 in alkaline, acidic, and neutral electrolytes, respectively. It also shows a remarkable balance between electrocatalytic activity and stability. Based on the distinguished catalytic performance of CoMoNiS-NF-31 toward HER and OER, we demonstrate a two-electrode electrolyzer performing water electrolysis over a wide pH range, with low cell voltages of 1.54, 1.45, and 1.80 V at 10 mA cm-2 in alkaline, acidic, and neutral media, respectively. First-principles calculations suggest that the high OER activity arises from electron transfer from Co9S8 to MoS2 at the interface, which alters the binding energies of adsorbed species and decreases overpotentials. Our results demonstrate that hierarchical metal sulfides can serve as highly efficient all-pH (pH = 0-14) electrocatalysts for overall water splitting.

3D Porous Amorphous γ-CrOOH on Ni Foam as Bifunctional Electrocatalyst for Overall Water Splitting.

The development of novel and highly efficient bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is an ongoing challenge. The Cr3+ cation has a special electronic configuration (t32ge0g), which facilitates charge transfer and electron capture. However, Cr-based materials applied on water-splitting electrocatalysis is still a research void up to now. Herein, a novel amorphous γ-CrOOH was developed as a bifunctional electrocatalyst toward overall water splitting for the first time. It shows extraordinary HER activity with an ultralow overpotential of only 149 mV at 50 mA cm-2. Meantime, there is a small overpotential of 334 mV at 50 mA cm-2 for the OER. Importantly, the bifunctional electrocatalyst for overall water-splitting electrocatalysis can work with a cell voltage of merely 1.56 V at 10 mA cm-2. Amorphous γ-CrOOH has effectively enhanced the intrinsic electrochemical activity via density functional theoretical calculations. Therefore, this work not only provides a new method for preparation of amorphous γ-CrOOH but also expands the types of catalysts for water splitting.