Confining High-Valence Iridium Single Sites onto Nickel Oxyhydroxide for Robust Oxygen Evolution.

Enhancing activity and stability of iridium- (Ir-) based oxygen evolution reaction (OER) catalysts is of great significance in practice. Here, we report a vacancy-rich nickel hydroxide stabilized Ir single-atom catalyst (Ir1-Ni(OH)2), which achieves long-term OER stability over 260 h and much higher mass activity than commercial IrO2 in alkaline media. In situ X-ray absorption spectroscopy analysis certifies the obvious structure reconstruction of catalyst in OER. As a result, an active structure in which high-valence and peripheral oxygen ligands-rich Ir sites are confined onto the nickel oxyhydroxide surface is formed. In addition, the precise introduction of atomized Ir not only surmounts the large-range dissolution and agglomeration of Ir but also suppresses the dissolution of substrate in OER. Theoretical calculations further account for the activation of Ir single atoms and the promotion of oxygen generation by high-valence Ir, and they reveal that the deprotonation process of adsorbed OH is rate-determining.

Reversible Al Metal Anodes Enabled by Amorphization for Aqueous Aluminum Batteries.

Aqueous aluminum metal batteries (AMBs) are regarded as one of the most sustainable energy storage systems among post-lithium-ion candidates, which is attributable to their highest theoretical volumetric capacity, inherent safe operation, and low cost. Yet, the development of aqueous AMBs is plagued by the incapable aluminum plating in an aqueous solution and severe parasitic reactions, which results in the limited discharge voltage, thus making the development of aqueous AMBs unsuccessful so far. Here, we demonstrate that amorphization is an effective strategy to tackle these critical issues of a metallic Al anode by shifting the reduction potential for Al deposition. The amorphous aluminum (a-Al) interfacial layer is triggered by an in situ lithium-ion alloying/dealloying process on a metallic Al substrate with low strength. Unveiled by experimental and theoretical investigations, the amorphous structure greatly lowers the Al nucleation energy barrier, which forces the Al deposition competitive to the electron-stealing hydrogen evolution reaction (HER). Simultaneously, the inhibited HER mitigates the passivation, promoting interfacial ion transfer kinetics and enabling steady aluminum plating/stripping for 800 h in the symmetric cell. The resultant multiple full cells using Al@a-Al anodes deliver approximately a 0.6 V increase in the discharge voltage plateau compared to that of bare Al-based cells, which far outperform all reported aqueous AMBs. In both symmetric cells and full cells, the excellent electrochemical performances are achieved in a noncorrosive, low-cost, and fluorine-free Al2(SO4)3 electrolyte, which is ecofriendly and can be easily adapted for sustainable large-scale applications. This work brings an intriguing picture of the design of metallic anodes for reversible and high-voltage AMBs.

In Situ Synthesis and Microfabrication of High Entropy Alloy and Oxide Compounds by Femtosecond Laser Direct Writing under Ambient Conditions.

Synthesis and coating of multi-metal oxides (MMOs) and alloys on conductive substrates are indispensable to electrochemical applications, yet demand multiple, resource-intensive, and time-consuming processes. Herein, an alternative approach to the synthesis and coating of alloys and MMOs by femtosecond laser direct writing (FsLDW) is reported. A solution-based precursor ink is deposited and dried on the substrate and illuminated by a femtosecond laser. During the illumination, dried precursor ink is transformed to MMO/alloys and is simultaneously bonded to the substrate. The formulation of the alloy and MMO precursor ink for laser processing is universally applicable to a large family of oxides and alloys. The process is conducted at room temperature and in an open atmosphere. To demonstrate, a large family of 57 MMOs and alloys are synthesized from a group of 13 elements. As a proof of concept, Ni0.24 Co0.23 Cu0.24 Fe0.15 Cr0.14 high entropy alloy synthesized on stainless-steel foil by FsLDW is used for the oxygen evolution reaction, which achieves a current density of 10 mA cm-2 at a significantly low overpotential of 213 mV. Further, FsLDW can also achieve microfabrication of alloys/MMO with feature sizes down to 20 µm.

Efficient and Selective CO2 Reduction to Formate on Pd-Doped Pb3 (CO3 )2 (OH)2 : Dynamic Catalyst Reconstruction and Accelerated CO2 Protonation.

Exploring catalyst reconstruction under the electrochemical condition is critical to understanding the catalyst structure-activity relationship as well as to design effective electrocatalysts. Herein, a PbF2 nanocluster is synthesized and its self-reconstruction under the CO2 reduction condition is investigated. F- leaching, CO2 -saturated environment, and application of a cathodic potential induce self-reconstruction of PbF2 to Pb3 (CO3 )2 (OH)2 , which effectively catalyze the CO2 reduction to formate. The in situ formed Pb3 (CO3 )2 (OH)2 discloses >80% formate Faradaic efficiencies (FEs) across a broad range of potentials and achieves a maximum formate FE of ≈90.1% at -1.2 V versus reversible hydrogen electrode (RHE). Kinetic studies show that the CO2 reduction reaction (CO2 RR) on the Pb3 (CO3 )2 (OH)2 is rate-limited at the CO2 protonation step, in which proton is supplied by bicarbonate (HCO3 - ) in the electrolyte. To improve the CO2 RR kinetics, the Pb3 (CO3 )2 (OH)2 is further doped with Pd (4 wt%) to enhance its HCO3 - adsorption, which leads to accelerated protonation of CO2 . Therefore, the Pd-Pb3 (CO3 )2 (OH)2 (4 wt%) reveals higher formate FEs of >90% from -0.8 to -1.2 V versus RHE and reaches a maximum formate FE of 96.5% at -1.2 V versus RHE with a current density of ≈13 mA cm-2 .

Dynamic Restructuring of Cu-Doped SnS2 Nanoflowers for Highly Selective Electrochemical CO2 Reduction to Formate.

With ever-increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO2 RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S-doping and Cu-alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2 RR.

An All-Organic D-A System for Visible-Light-Driven Overall Water Splitting.

Direct water splitting over photocatalysts is a prospective strategy to convert solar energy into hydrogen energy. Nevertheless, because of the undesirable electron accumulation at the surface, the overall water-splitting efficiency is seriously restricted by the poor charge separation/transfer ability. Here, an all-organic donor-acceptor (D-A) system through crafting carbon rings units-conjugated tubular graphitic carbon nitride (C-TCN) is proposed. Through a range of characterizations and theoretical calculations, the incorporation of carbon rings units via continuous π-conjugated bond builds a D-A system, which can drive intramolecular charge transfer to realize highly efficient charge separation. More importantly, the tubular structure and the incorporated carbon rings units cause a significant downshift of the valence band, of which the potential is beneficial to the activation for O2 evolution. When serving as photocatalyst for overall water splitting, C-TCN displays considerable performance with H2 and O2 production rates of 204.6 and 100.8 µmol g-1 h-1 , respectively. The corresponding external quantum efficiency reaches 2.6% at 405 nm, and still remains 1.7% at 420 nm. This work demonstrates that the all-organic D-A system conceptualized from organic solar cell can offer promotional effect for overall water splitting by addressing the charge accumulation problem rooted in the hydrogen evolution reaction.

Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single-Atom Catalysts.

The electrochemical CO2 reduction reaction (CO2 RR) to yield synthesis gas (syngas, CO and H2 ) has been considered as a promising method to realize the net reduction in CO2 emission. However, it is challenging to balance the CO2 RR activity and the CO/H2 ratio. To address this issue, nitrogen-doped carbon supported single-atom catalysts are designed as electrocatalysts to produce syngas from CO2 RR. While Co and Ni single-atom catalysts are selective in producing H2 and CO, respectively, electrocatalysts containing both Co and Ni show a high syngas evolution (total current >74 mA cm-2 ) with CO/H2 ratios (0.23-2.26) that are suitable for typical downstream thermochemical reactions. Density functional theory calculations provide insights into the key intermediates on Co and Ni single-atom configurations for the H2 and CO evolution. The results present a useful case on how non-precious transition metal species can maintain high CO2 RR activity with tunable CO/H2 ratios.

Stereodefined Codoping of sp-N and S Atoms in Few-Layer Graphdiyne for Oxygen Evolution Reaction.

Developing metal-free catalysts with high catalytic activity for oxygen evolution reaction (OER) is essentially important for energy and environment-related techniques. Compared with individual element doping, doping carbon materials with multiple heteroelements has more advantages for enhancing the OER performance. However, doped sites for the different atoms are highly uncontrollable under the reported methods, which hinder the deeper understanding on the relationship between structure and property, and also limit the enhancement of catalytic activity. Our latest research has reported a method to site-controlled introducing a new form of nitrogen atoms, i.e. sp-hybridized nitrogen (sp-N), into graphdiyne, showing its potential advantages in OER catalysis. Since the sites of sp-N atoms are defined in graphdiyne, and the doping sites for S atoms are well understood, the relative position between N and S can be further defined. It gives us a chance to understand deeply the mechanism in the N, S heteroelements doped metal-free catalyst. Experimental results present that the codoping of sp-N and S atoms brought an excellent OER performance with low overpotential and high current density owning to the effectively synergistic effect of the stereodefined heteroatoms.

Reversible Oxygen Redox Chemistry in Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) are promising energy-storage devices owing to their low cost and high safety. However, their energy-storage mechanisms are complex and not well established. Recent energy-storage mechanisms of ZIBs usually depend on cationic redox processes. Anionic redox processes have not been observed owing to the limitations of cathodes and electrolytes. Herein, we describe highly reversible aqueous ZIBs based on layered VOPO4 cathodes and a water-in-salt electrolyte. Such batteries display reversible oxygen redox chemistry in a high-voltage region. The oxygen redox process not only provides about 27 % additional capacity, but also increases the average operating voltage to around 1.56 V, thus increasing the energy density by approximately 36 %. Furthermore, the oxygen redox process promotes the reversible crystal-structure evolution of VOPO4 during charge/discharge processes, thus resulting in enhanced rate capability and cycling performance.

Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.

All-Carbon Ultrafast Supercapacitor by Integrating Multidimensional Nanocarbons.

Ultrafast and high capacity all-carbon supercapacitors with 3D porous aerogel electrode are realized by combining carbon nanostructures of various dimensionalities, including 0D carbon onions, 1D carbon nanotubes, and 2D graphene oxide. The synergistic effects from the different forms of nanocarbons render this hybrid outstanding capacitance with excellent stability, even at ultrafast charge-discharge rates.

Designing hierarchical hollow nanostructures of Cu2MoS4 for improved hydrogen evolution reaction.

Layered Cu2MoS4, consisting of earth-abundant elements, is regarded as a potential catalyst for the hydrogen evolution reaction (HER). Herein, we demonstrate a Cu2O-based template strategy to synthesise hierarchical hollow nanostructures of Cu2MoS4. The characterizations reveal that the electrochemically active surface of the hollow Cu2MoS4 is largely enhanced, in contrast to the nanosheet or nanoparticle structures. As the direct outcome, the designed hierarchical hollow structures display excellent HER activities with a low overvoltage and small Tafel slope. This study may provide new inspiration for the research of other ternary sulphide materials as well as subsequently accelerating their applications in the field of catalysis.

Growing and Etching MoS2 on Carbon Nanotube Film for Enhanced Electrochemical Performance.

In this work we directly synthesized molybdenum disulfide (MoS2) nanosheets on carbon nanotube film (MoS2@CNT) via a two-step chemical vapor deposition method (CVD). By etching the obtained MoS2@CNT into 10% wt HNO3, the morphology of MoS2 decorated on CNT bundles was modulated, resulting in more catalytic active MoS2 edges being exposed for significantly enhanced electrochemical performance. Our results revealed that an 8 h acid etching sample exhibited the best performance for the oxygen evolution reaction, i.e., the current density reached 10 mA/cm² under 375 mV over-potential, and the tafel slope was as low as 94 mV/dec. The enhanced behavior was mainly originated from the more catalytic sites in MoS2 induced by the acid etching treatment and the higher conductivity from the supporting CNT films. Our study provides a new route to produce two-dimensional layers on CNT films with tunable morphology, and thus may open a window for exploring its promising applications in the fields of catalytic-, electronic-, and electrochemical-related fields.

Gram-Scale Aqueous Synthesis of Stable Few-Layered 1T-MoS2 : Applications for Visible-Light-Driven Photocatalytic Hydrogen Evolution.

Most recently, much attention has been devoted to 1T phase MoS2 because of its distinctive phase-engineering nature and promising applications in catalysts, electronics, and energy storage devices. While alkali metal intercalation and exfoliation methods have been well developed to realize unstable 1T-MoS2 , but the aqueous synthesis for producing stable metallic phase remains big challenging. Herein, a new synthetic protocol is developed to mass-produce colloidal metallic 1T-MoS2 layers highly stabilized by intercalated ammonium ions (abbreviated as N-MoS2). In combination with density functional calculations, the X-ray diffraction pattern and Raman spectra elucidate the excellent stability of metallic phase. As clearly depicted by high-angle annular dark-field imaging in an aberration-corrected scanning transmission electron microscope and extended X-ray absorption fine structure, the N-MoS2 exhibits a distorted octahedral structure with a 2a0 × a0 basal plane superlattice and 2.72 Å Mo-Mo bond length. In a proof-of-concept demonstration for the obtained material's applications, highly efficient photocatalytic activity is achieved by simply hybridizing metallic N-MoS2 with semiconducting CdS nanorods due to the synergistic effect. As a direct outcome, this CdS:N-MoS2 hybrid shows giant enhancement of hydrogen evolution rate, which is almost 21-fold higher than pure CdS and threefold higher than corresponding annealed CdS:2H-MoS2.

Efficient Electrocatalyst Nanoparticles from Upcycled Class II Capacitors.

To move away from fossil fuels, the electrochemical reaction plays a critical role in renewable energy sources and devices. The anodic oxygen evolution reaction (OER) is always coupled with these reactions in devices but suffers from large energy barriers. Thus, it is important for developing efficient OER catalysts with low overpotential. On the other hand, there are large amounts of metals in electronic waste (E-waste), especially various transition metals that are promising alternatives for catalyzing OER. Hence, this work, which focuses on upcycling Class II BaTiO3 Multilayer Ceramic Capacitors, of which two trillion were produced in 2011 alone. We achieved this by first using a green solvent extraction method that combined the ionic liquid Aliquat® 336 and hydrochloride acid to recover a mixed solution of Ni, Fe and Cu cations, and then using such a solution to synthesize high potential catalysts NiFe hydroxide and NiCu hydroxide for OER. NiFe-hydroxide has been demonstrated to have faster OER kinetics than the NiCu-hydroxide and commercial c-RuO2. In addition, it showed promising results after the chronopotentiometry tests that outperform c-RuO2.

Synergic Reaction Kinetics over Adjacent Ruthenium Sites for Superb Hydrogen Generation in Alkaline Media.

Ruthenium (Ru)-based electrocatalysts as platinum (Pt) alternatives in catalyzing hydrogen evolution reaction (HER) are promising. However, achieving efficient reaction processes on Ru catalysts is still a challenge, especially in alkaline media. Here, the well-dispersed Ru nanoparticles with adjacent Ru single atoms on carbon substrate (Ru1,n -NC) is demonstrated to be a superb electrocatalyst for alkaline HER. The obtained Ru1,n -NC exhibits ultralow overpotential (14.8 mV) and high turnover frequency (1.25 H2  s-1 at -0.025 V vs reversible hydrogen electrode), much better than the commercial 40 wt.% Pt/C. The analyses reveal that Ru nanoparticles and single sites can promote each other to deliver electrons to the carbon substrate. Eventually, the electronic regulations bring accelerated water dissociation and reduced energy barriers of hydroxide/hydrogen desorption on adjacent Ru sites, then an optimized reaction kinetics for Ru1,n -NC is obtained to achieve superb hydrogen generation in alkaline media. This work provides a new insight into the catalyst design in simultaneous optimizations of the elementary steps to obtain ideal HER performance in alkaline media.

Anomalous self-optimization of sulfate ions for boosted oxygen evolution reaction.

Broadly, the oxygen evolution reaction (OER) has been deeply understood as a significant part of energy conversion and storage. Nevertheless, the anions in the OER catalysts have been neglected for various reasons such as inactive sites, dissolution, and oxidation, amongst others. Herein, we applied a model catalyst s-Ni(OH)2 to track the anionic behavior in the catalyst during the electrochemical process to fill this gap. The advanced operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy, synchrotron radiation photoelectron spectroscopy (SRPES) depth detection and differential X-ray absorption fine structure (Δ-XAFS) spectrum jointly point out that some oxidized sulfur species (SO42-) will self-optimize new Ni-S bonds during OER process. Such amazing anionic self-optimization (ASO) behavior has never been observed in the OER process. Subsequently, the optimization-derived component shows a significantly improved electrocatalytic performance (activity, stability, etc.) compared to reference catalyst Ni(OH)2. Theoretical calculation further suggests that the ASO process indeed derives a thermodynamically stable structure of the OER catalyst, and then gives its superb catalytic performance by optimizing the thermodynamic and kinetic processes in the OER, respectively. This work demonstrates the vital role of anions in the electrochemical process, which will open up new perspectives for understanding OER and provide some new ideas in related fields (especially catalysis and chemistry).

Facile and eco-friendly preparation of super-amphiphilic porous polycaprolactone.

Super-amphiphilic (highly oleophilic and hydrophilic) materials have attracted tremendous interest for fundamental research and potential applications, owing to their unique affinity for both oil and water. In this work, a novel super-amphiphilic porous polycaprolactone (PCL) was fabricated via an efficient and eco-friendly method, in which stearic acid (SA) was used as both a porogen and a dopant precursor. The porous PCL had an interconnected hierarchical pore structure and was capable of absorbing oil and water rapidly. The complementary cooperation of the oleophilic and hydrophilic domains on the pore surface induced the amphiphilicity, while the capillary forces caused a wicking action. The synergy of the two effects gave rise to the super-wetting property. The special amphiphilic feature of the porous PCL had a positive effect on its biocompatibility and the material can be considered as a promising candidate for tissue engineering applications.

A Unique Ru-N4-P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production.

Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N4-P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N4-P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-Hads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.

Achieving Efficient Alkaline Hydrogen Evolution Reaction over a Ni5 P4 Catalyst Incorporating Single-Atomic Ru Sites.

Developing efficient electrocatalysts for alkaline water electrolysis is central to substantial progress of alkaline hydrogen production. Herein, a Ni5 P4 electrocatalyst incorporating single-atom Ru (Ni5 P4 -Ru) is synthesized through the filling of Ru3+ species into the metal vacancies of nickel hydroxides and subsequent phosphorization treatment. Electron paramagnetic resonance spectroscopy, X-ray-based measurements, and electron microscopy observations confirm the strong interaction between the nickel-vacancy defect and Ru cation, resulting in more than 3.83 wt% single-atom Ru incorporation in the obtained Ni5 P4 -Ru. The Ni5 P4 -Ru as an alkaline hydrogen evolution reaction catalyst achieves low onset potential of 17 mV and an overpotential of 54 mV at a current density of 10 mA cm-2 together with a small Tafel slope of 52.0 mV decade-1 and long-term stability. Further spectroscopy analyses combined with density functional theory calculations reveal that the doped Ru sites can cause localized structure polarization, which brings the low energy barrier for water dissociation on Ru site and the optimized hydrogen adsorption free energy on the interstitial site, well rationalizing the experimental reactivity.