Rationally Designed L12-Pt2RhFe Intermetallic Catalyst with High CO-Tolerance for Alkaline Methanol Electrooxidation.

It is a grand challenge to deep understanding of and precise control over functional sites for the rational design of highly efficient catalysts for methanol electrooxidation. Here, an L12-Pt2RhFe intermetallic catalyst with integrated functional components is demonstrated, which exhibits exceptional CO tolerance. The Pt2RhFe/C achieves a superior mass activity of 6.43 A mgPt -1, which is 2.23-fold and 3.53-fold higher than those of PtRu/C and Pt/C. Impressively, the Pt2RhFe/C exhibits a significant enhancement in durability owing to its high CO-tolerance and stability. Density functional theory calculations reveal that high performance of Pt2RhFe intermetallic catalyst arises from the synergistic effect: the strong OH binding energy (OHBE) at Fe sites induce stably adsorbed OH species and thus facilitate the dehydrogenation step of methanol via rapid hydrogen transfer, while moderate OHBE at Rh sites promote the formation of the transition state (Pt-CO···OH-Rh) with a low activation barrier for CO removal. This work provides new insights into the role of OH binding strength in the removal of CO species, which is beneficial for the rational design of highly efficient catalysts.

Mitigating Strain Accumulation in Li2RuO3 via Fluorine Doping.

Lithium ruthenium oxide (Li2RuO3) is an archetypal lithium rich cathode material (LRCM) with both cation and anion redox reactions (ARRs). Commonly, the instability of oxygen redox activities has been regarded as the root cause of its performance degradation in long-term operation. However, we find that not triggering ARRs does not improve and even worsens its cyclability due to the detrimental strain accumulation induced by Ru redox activities. To solve this problem, we demonstrate that F-doping in Li2RuO3 can alter its preferential orientation and buffer interlayer repulsion upon Ru redox, both of which can mitigate the strain accumulation along the c-axis and improve its structural stability. This work highlights the importance of optimizing cation redox reactions in LRCMs and provides a new perspective for their rational design.

Pt1.8Pd0.2CuGa Intermetallic Nanocatalysts with Enhanced Methanol Oxidation Performance for Efficient Hybrid Seawater Electrolysis.

Seawater electrolysis is a potentially cost-effective approach to green hydrogen production, but it currently faces substantial challenges for its high energy consumption and the interference of chlorine evolution reaction (ClER). Replacing the energy-demanding oxygen evolution reaction with methanol oxidation reaction (MOR) represents a promising alternative, as MOR occurs at a significantly low anodic potential, which cannot only reduce the voltage needed for electrolysis but also completely circumvents ClER. To this end, developing high-performance MOR catalysts is a key. Herein, a novel quaternary Pt1.8Pd0.2CuGa/C intermetallic nanoparticle (i-NP) catalyst is reported, which shows a high mass activity (11.13 A mgPGM -1), a large specific activity (18.13 mA cmPGM -2), and outstanding stability toward alkaline MOR. Advanced characterization and density functional theory calculations reveal that the introduction of atomically distributed Pd in Pt2CuGa intermetallic markedly promotes the oxidation of key reaction intermediates by enriching electron concentration around Pt sites, resulting in weak adsorption of carbon-containing intermediates and favorable adsorption of synergistic OH- groups near Pd sites. MOR-assisted seawater electrolysis is demonstrated, which continuously operates under 1.23 V for 240 h in simulated seawater and 120 h in natural seawater without notable degradation.

Dependence of Interlayer or Sulfur Host on Hollow Framework of Lithium-Sulfur Battery.

Lithium-sulfur batteries are recognized as the next generation of high-specific energy secondary batteries owing to their satisfactory theoretical specific capacity and energy density. However, their commercial application is greatly limited by a series of problems, including disordered migration behavior, sluggish redox kinetics, and the serious shuttle effect of lithium polysulfides. One of the most efficient approaches to physically limit the shuttle effect is the rational design of a hollow framework as sulfur host. However, the influence of the hollow structure on the interlayers has not been clearly reported. In this study, the Mo2 C/C catalysts with hollow(H-Mo2 C/C) and solid(S-Mo2 C/C) frameworks are rationally designed to explore the dependence of the hollow structure on the interlayer or sulfur host. In contrast to the physical limitations of the hollow framework as host, the hollow structure of the interlayer inhibited lithium-ion diffusion, resulting in poor electrochemical properties at high current densities. Based on the superiority of the various frameworks, the H-Mo2 C/C@S | S-Mo2 C/C@PP | Li cells are assembled and displayed excellent electrochemical performance. This work re-examines the design requirements and principles of catalyst frameworks in different battery units.

Regulating Au coverage for the direct oxidation of methane to methanol.

The direct oxidation of methane to methanol under mild conditions is challenging owing to its inadequate activity and low selectivity. A key objective is improving the selective oxidation of the first carbon-hydrogen bond of methane, while inhibiting the oxidation of the remaining carbon-hydrogen bonds to ensure high yield and selectivity of methanol. Here we design ultrathin PdxAuy nanosheets and revealed a volcano-type relationship between the binding strength of hydroxyl radical on the catalyst surface and catalytic performance using experimental and density functional theory results. Our investigations indicate a trade-off relationship between the reaction-triggering and reaction-conversion steps in the reaction process. The optimized Pd3Au1 nanosheets exhibits a methanol production rate of 147.8 millimoles per gram of Pd per hour, with a selectivity of 98% at 70 °C, representing one of the most efficient catalysts for the direct oxidation of methane to methanol.

Fabrication of highly efficient Rh-doped cobalt-nickel-layered double hydroxide/MXene-based electrocatalyst with rich oxygen vacancies for hydrogen evolution.

The development of nonprecious metal catalysts for producing hydrogen from economical alkaline water electrolysis that is both stable and efficient is crucial but remains challenging. In this study, Rh-doped cobalt-nickel-layered double hydroxide (CoNi LDH) nanosheet arrays with abundant oxygen vacancies (Ov) in-situ grown on Ti3C2Tx MXene nanosheets (Rh-CoNi LDH/MXene) were successfully fabricated. The synthesized Rh-CoNi LDH/MXene exhibited excellent long-term stability and a low overpotential of 74.6 ± 0.4 mV at -10 mA cm-2 for hydrogen evolution reaction (HER) owing to its optimized electronic structure. Experimental results and density functional theory calculations revealed that the incorporation of Rh dopant and Ov into CoNi LDH and the coupling interface between Rh-CoNi LDH and MXene optimized the hydrogen adsorption energy, which accelerated the hydrogen evolution kinetics, thereby accelerating the overall alkaline HER process. This work presents a promising strategy for designing and synthesizing highly efficient electrocatalysts for electrochemical energy conversion devices.

Dilute Alloying to Implant Activation Centers in Nitride Electrocatalysts for Lithium-Sulfur Batteries.

Dilute alloying is an effective strategy to tune properties of solid catalysts but is rarely leveraged in complex reactions beyond small molecule conversion. In this work, dilute dopants are demonstrated to serve as activating centers to construct multiatom catalytic domains in metal nitride electrocatalysts for lithium-sulfur (Li-S) batteries, of which the sulfur cathode suffers from sluggish and complex conversion reactions. With titanium nitride (TiN) as a model system, the dilute cobalt alloying is shown to greatly improve the reaction kinetics while inducing negligible catalyst reconstruction. Compared to the pristine TiN, the dilute nitride alloy catalyst enables onefold increase in the high rate (2.0 C) capacities of Li-S batteries, as well as an impressively low cyclic decay rate of 0.17% at a sulfur loading of 4.0 mgS cm-2 . This work opens up new opportunities toward the rational design of Li-S electrocatalysts by dilute alloying and also enlightens the understandings of complex domain-catalyzed reactions in energy applications.

Achieving job-synergistic polysulfides adsorption-conversion within hollow structured MoS2/Co4S3/C heterojunction host for long-life lithium-sulfur batteries.

Lithium-sulfur batteries are considered one of the most promising next-generation energy storage devices owing to their ultrahigh theoretical energy density and environmental friendliness. However, the sluggish electrode reaction kinetics of the sulfur cathode and shuttle effects of lithium polysulfide (LiPSs) restrict their active material utilization and cycling stability. Herein, a hollow, free-standing MoS2/Co4S3/C heterojunction was fabricated and employed as a cathode host for high-performance lithium-sulfur batteries (LSBs). The unique hollow nanostructured MoS2/Co4S3/C can achieve job-synergistic polysulfide adsorption-conversion, in which the conductive nitrogen-doped carbon framework facilitates rapid electron/ion diffusion; polar Co4S3 species provide strong chemisorption capability and endow intrinsic catalytic sites towards LiPSs, and MoS2 serves as a nanocrystal to accelerate the reaction dynamics. As a result, MoS2/Co4S3/C/S exhibited high reversible specific capacities at 2C and was maintained at 394 mAh g-1 after 1000 cycles, with a 0.04% capacity decay rate. Impressively, the high reversible specific capacities with high sulfur loading of 4.1 mg cm-2 were maintained at 906.7 mAh g-1.

Modulating the Acidic Properties of Mesoporous Mox-Ni0.8Cu0.2O Nanowires for Enhanced Catalytic Performance toward the Methanolysis of Ammonia Borane for Hydrogen Production.

Rational construction of inexpensive, highly efficient, and stable catalysts for ammonia borane (AB) methanolysis is in high demand but still remains a great challenge. In this work, we have successfully fabricated uniform Mox-Ni0.8Cu0.2O nanowires using a simple hydrothermal method followed by a post-calcination treatment and flexibly modulated the acidity of their surface by changing the amount of Mo introduced into Ni0.8Cu0.2O. The Mo0.1-Ni0.8Cu0.2O catalyst displayed strong catalytic activity toward AB methanolysis with an ultrahigh turnover frequency of 46.9 molH2 molcat.-1 min-1, which is even higher than some noble metal catalysts. In this work, an equation regarding the relationship between the quantity of moderated acid sites of catalysts and its corresponding activity toward AB methanolysis was first determined. A plausible mechanism for AB methanolysis catalyzed by Mox-Ni0.8Cu0.2O was proposed, and the benefits of the introduction of MoO3 to Ni0.8Cu0.2O for enhancing the catalytic performance were also discussed. These findings can form a basis for the rational construction of inexpensive catalysts with robust performance toward AB methanolysis for hydrogen production.

Modification of Nitrate Ion Enables Stable Solid Electrolyte Interphase in Lithium Metal Batteries.

The lifespan of high-energy-density lithium metal batteries (LMBs) is hindered by heterogeneous solid electrolyte interphase (SEI). The rational design of electrolytes is strongly considered to obtain uniform SEI in working batteries. Herein, a modification of nitrate ion (NO3 - ) is proposed and validated to improve the homogeneity of the SEI in practical LMBs. NO3 - is connected to an ether-based moiety to form isosorbide dinitrate (ISDN) to break the resonance structure of NO3 - and improve the reducibility. The decomposition of non-resonant -NO3 in ISDN enriches SEI with abundant LiNx Oy and induces uniform lithium deposition. Lithium-sulfur batteries with ISDN additives deliver a capacity retention of 83.7 % for 100 cycles compared with rapid decay with LiNO3 after 55 cycles. Moreover, lithium-sulfur pouch cells with ISDN additives provide a specific energy of 319 Wh kg-1 and undergo 20 cycles. This work provides a realistic reference in designing additives to modify the SEI for stabilizing LMBs.

Co4 N-Decorated 3D Wood-Derived Carbon Host Enables Enhanced Cathodic Electrocatalysis and Homogeneous Lithium Deposition for Lithium-Sulfur Full Cells.

The sluggish kinetics of sulfur conversion in the cathode and the nonuniform deposition of lithium metal at the anode result in severe capacity decay and poor cycle life for lithium-sulfur (Li-S) batteries. Resolving these deficiencies is the most direct route toward achieving practical cells of this chemistry. Herein, a vertically aligned wood-derived carbon plate decorated with Co4 N nanoparticles host (Co4 N/WCP) is proposed that can serve as a host for both the sulfur cathode and the metallic lithium anode. This Co4 N/WCP electrode host drastically enhances the reaction kinetics in the sulfur cathode and homogenizes the electric field at the anode for the uniform lithium plating. Density functional theory calculations confirm the experimental observations that Co4 N/WCP provides a lower energy barrier for the polysulfide redox reaction in the cathode and a low adsorption energy for lithium deposition at the anode. Employing the Co4 N/WCP host at both electrodes in a S@Co4 N/WCP||Li@Co4 N/WCP full cell delivers a specific capacity of 807.9 mAh g-1 after 500 cycles at a 1 C rate. Additional experiments are performed with high areal sulfur loading of 4 mg cm-2 to demonstrate the viability of this strategy for producing practical Li-S cells.

Balanced capture and catalytic ability toward polysulfides by designing MoO2-Co2Mo3O8 heterostructures for lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries, as the next generation of energy storage systems, are currently limited by insufficient capture ability and sluggish catalytic reaction kinetics, thus leading to serve the shuttle effect of lithium polysulfides (LiPSs). Realizing the accelerated conversion of polysulfides in the cathode host of Li-S batteries is an effective way to improve its coulombic efficiency. The essence of fast conversion relies on enhanced oxidation reaction kinetics by virtue of the metal catalyst, but the generation of various intermediates exacerbate the complexity of the system and perplex the perfect operation of batteries relying on only one catalyst. In this work, the xMoO2:yCo2Mo3O8 heterostructures were designed, in which controlling the content of cobalt could balance the capture capability towards LiPSs by MoO2 and catalytic ability of liquid-solid conversion by Co2Mo3O8 catalytic sites. Therefore, utilizing synergy effect of MoO2-Co2Mo3O8 heterostructure enhances capture and catalytic ability toward polysulfides in Li-S batteries. As a result, the 9MoO2:2Co2Mo3O8-based cathode delivers excellent reversibility of 880 mA h g-1 after 100 cycles at 0.2C and 509 mA h g-1 after 1000 cycles at 1C with 0.056% capacity decay each cycle. This work provides a new method for synthesizing heterostructures by doping metals. Moreover, it promotes the understanding of balancing and promoting the capture capacity and catalytic conversion ability toward LiPSs.

Direct Utilization of Photoinduced Charge Carriers to Promote Electrochemical Energy Storage.

Electrochemical energy storage has been regarded as one of the most promising strategies for next-generation energy consumption. To meet the increasing demands of urban electric vehicles, development of green and efficient charging technologies by exploitation of solar energy should be considered for outdoor charging in the future. Herein, a light-sensitive material (copper foam-supported copper oxide/nickel copper oxides nanosheets arrays, namely CF@CuOx @NiCuOx NAs) with hierarchical nanostructures to promote electrochemical charge storage is specifically fabricated. The as-fabricated NAs have demonstrated a high areal specific capacity of 1.452 C cm-2 under light irradiation with a light power of 1.76 W, which is 44.8% higher than the capacity obtained without light. Such areal specific capacity (1.452 C cm-2 ) is much higher than that of the conventional supercapacitor structure using a similar active redox component reported recently (NiO nanosheets array@Co3 O4 -NiO FTNs: maximum areal capacity of 623.5 mF cm-2 at 2 mA cm-2 ). This photo-enhancement for charge storage can be attributed to the combination of photo-sensitive Cu2 O and pseudo-active NiO components. Hence, this work may provide new possibilities for direct utilization of sustainable solar energy to realize enhanced capability for energy storage devices.

Materials Engineering in Perovskite for Optimized Oxygen Evolution Electrocatalysis in Alkaline Condition.

Developing robust and highly efficient electrocatalysts for oxygen evolution reaction (OER) is critical for renewable, secure, and emission-free energy technologies. Perovskite Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ (BSCF) has emerged as a promising OER electrocatalyst with desirable intrinsic activity. Inspired by the factor that substituting in transition-metal sublattice of the perovskite can further optimize the OER activity, herein, nickel-substituted BSCF is adopted, that is, Ba0.5 Sr0.5 Co0.8- x Fe0.2 Nix O3-δ (x = 0.05, 0.1, 0.2, denoted as BSCFNx, x = 5, 10, 20, respectively), as efficient and stable OER catalysts in alkaline solution. The phase structure, microchemistry, oxygen vacancy, and electrochemical activity of such samples are well-investigated. Endowed with an overpotential of only 278 mV at 10 mA cm-2 and a Tafel slope of merely 47.98 mV dec-1 , BSCFN20 exhibits the optimum OER activity. When constructing a two-electrode cell with BSCFN20 as anode and Pt/C as cathode (BSCFN20||Pt/C) for water splitting, it only requires a voltage of 1.63 V to achieve 50 mA cm-2 , and the BSCFN20||Pt/C remains stable within 80 h at 10 mA cm-2 , superior to the state-of-the-art RuO2 ||Pt/C counterpart. This work provides a feasible strategy for designing stable and highly active perovskite electrocatalysts for future energy storage and conversion.

Nonstoichiometric Cu0.6Ni0.4Co2O4 Nanowires as an Anode Material for High Performance Lithium Storage.

Transition metal oxide is one of the most promising anode materials for lithium-ion batteries. Generally, the electrochemical property of transition metal oxides can be improved by optimizing their element components and controlling their nano-architecture. Herein, we designed nonstoichiometric Cu0.6Ni0.4Co2O4 nanowires for high performance lithium-ion storage. It is found that the specific capacity of Cu0.6Ni0.4Co2O4 nanowires remain 880 mAh g-1 after 50 cycles, exhibiting much better electrochemical performance than CuCo2O4 and NiCo2O4. After experiencing a large current charge and discharge state, the discharge capacity of Cu0.6Ni0.4Co2O4 nanowires recovers to 780 mAh g-1 at 50 mA g-1, which is ca. 88% of the initial capacity. The high electrochemical performance of Cu0.6Ni0.4Co2O4 nanowires is related to their better electronic conductivity and synergistic effect of metals. This work may provide a new strategy for the design of multicomponent transition metal oxides as anode materials for lithium-ion batteries.

Engineering the electronic and strained interface for high activity of PdMcore@Ptmonolayer electrocatalysts for oxygen reduction reaction.

Alloyed nanoparticles with core-shell structures provide a favorable model to modulate interfacial interaction and surface structures at the atomic level, which is important for designing electrocatalysts with high activity and durability. Herein, core-shell structured Pd3M@Pt/C nanoparticles with binary PdM alloy cores (M = Fe, Ni, and Co) and a monolayer Pt shell were successfully synthesized with diverse interfaces. Among these, Pd3Fe@Pt/C exhibited the best oxygen reduction reaction catalytic performance, roughly 5.4 times more than that of the commercial Pt/C catalyst used as reference. The significantly enhanced activity is attributed to the combined effects of strain engineering, interfacial electron transfer, and improved Pt utilization. Density functional theory simulations and extended X-ray absorption fine structure analysis revealed that engineering the alloy core with moderate lattice mismatch and alloy composition (Pd3Fe) optimizes the surface oxygen adsorption energy, thereby rendering excellent electrocatalytic activity. Future researches may use this study as a guide on the construction of highly effective core-shell electrocatalysts for various energy conversions and other applications.

Rational Design of an Ionic Liquid-Based Electrolyte with High Ionic Conductivity Towards Safe Lithium/Lithium-Ion Batteries.

It is a very urgent and important task to improve the safety and high-temperature performance of lithium/lithium-ion batteries (LIBs). Here, a novel ionic liquid, 1-(2-ethoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR1(2o2) TFSI), was designed and synthesized, and then mixed with dimethyl carbonate (DMC) as appropriate solvent and LiTFSI lithium salt to produce an electrolyte with high ionic conductivity for safe LIBs. Various characterizations and tests show that the highly flexible ether group could markedly reduce the viscosity and provide coordination sites for Li-ion, and the DMC could reduce the viscosity and effectively enhance the Li-ion transport rate and transference number. The electrolyte exhibits excellent electrochemical performance in Li/LiFeO4 cells at room temperature as well as at a high temperature of 60 °C. More importantly, with the addition of DMC, the IL-based electrolyte remains nonflammable and appropriate DMC can effectively inhibit the growth of lithium dendrites. Our present work may provide an attractive and promising strategy for high performance and safety of both lithium and lithium-ion batteries.

A Simple and Scalable Route to Synthesize Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 Yolk-Shell Microspheres, A High-Performance Catalyst to Hydrolyze Ammonia Borane for Hydrogen Production.

Yolk-shell structured micro/nano-sized materials have broad and important applications in different areas due to their unique spatial configurations. In this study, yolk-shell structured Co3 O4 @Co3 O4 is prepared using a simple and scalable hydrothermal reaction, followed by a calcination process. Then, Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres are synthesized via adsorption and calcination processes using the as-prepared Co3 O4 @Co3 O4 as the precursor. A possible formation mechanism of the yolk-shell structures is proposed based on the characterization results, which is different from those of yolk-shell structures in previous study. For the first time, the catalytic activity of yolk-shell structured catalysts in ammonia borane (AB) hydrolysis is studied. It is discovered that the yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres exhibit high performance with a turnover frequency (TOF) of 81.8 molhydrogen min-1 molcat -1 . This is one of the highest TOF values reported for a noble-metal-free catalyst in the literature. Additionally, the yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microspheres are highly stable and reusable. These yolk-shell structured Cox Cu1- x Co2 O4 @Coy Cu1- y Co2 O4 microsphere is a promising catalyst candidate in AB hydrolysis considering the excellent catalytic behavior and low cost.

Tuning the Catalytic Activity of Ir@Pt Nanoparticles Through Controlling Ir Core Size on Cathode Performance for PEM Fuel Cell Application.

Pulse electrochemically synthesis of a series of core-shell structured Ir@Pt/C catalysts in cathode catalysts layer are achieved to fabricate membrane electrode assemblies (MEA) with cathode ultra-low Pt loading. The single cell performance of the MEAs in a H2/air PEMFC greatly rely on the sizes of the Ir core nanoparticle, and the optimum activity occurs with Ir core size of 4.1 nm. The cathode MEA with core-shell structured catalysts with optimal Ir core size exhibited excellent performance in a H2/air single fuel cell, comparable to that of a commercial Pt/C MEA (Johnson Matthey 40% Pt), even though the Pt loading in Ir@Pt was only 40% that of the commercial Pt cathode (0.04 vs. 0.1 mg cm-2). The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy. Based on the characterization results, especially from XPS, we suggest that the effect of Ir core particle size on MEA performance may arise from the interactions between the Pt shell and the Ir core. The XPS results showed that the Ir@Pt/C-300 catalyst has the highest Pt0 fraction among the four tested samples. This work demonstrates the alternative to enhance the cathode performance in single cell of Pt-based core-shell structured catalysts by varying size of the core metal under the Pt shell.