Activating nickel foam with trace titanium oxide for enhanced water oxidation.

Nickel-based electrocatalysts for water oxidation suffer from low activity and poor stability. In this work, 0.015 mg cm-2 TiO2 nanosheets anchored on Ni foam addressed these problems after electrochemical activation. In situ investigations, including Raman spectra, corroborated the enhanced generation of highly active Ni(III)-O-O species on Ni foam in the presence of trace TiO2.

Dynamic Restructuring of Cu7S4/Cu for Efficient CO2 Electro-reduction to Formate.

Optimized catalytic properties and reactant adsorption energy played a crucial role in promoting CO2 electrocatalysis. Herein, Cu7S4/Cu underwent in situ dynamic restructuring to generate S-Cu2O/Cu hybrid catalyst for effective electrochemical CO2 reduction to formate that outperformed Cu2O/Cu and Cu7S4. Thermodynamic and in situ Raman spectra revealed that the optimized adsorption of the HCOO* intermediate on S-Cu2O/Cu was regulated and the H2 pathway (surface H) was suppressed by S-doping. Meanwhile, Cu7S4/Cu nanoflowers created abundant boundaries for ECR and strengthened the CO2 adsorption by inducing Cu. These findings provide a new perspective on synthetic methods for various electrocatalytic reduction processes.

Semicrystalline IrOx with Abundant Boundaries for Overall Water Splitting.

Inorganic compounds with different crystalline and amorphous states may show distinct properties in catalytic applications. In this work, we control the crystallization level by fine thermal treatment and synthesize a semicrystalline IrOx material with the formation of abundant boundaries. Theoretical calculation reveals that the interfacial iridium with a high degree of unsaturation is highly active for the hydrogen evolution reaction compared to individual counterparts based on the optimal binding energy with hydrogen (H*). At the heat treatment temperature of 500 °C, the obtained IrOx-500 catalyst has dramatically promoted hydrogen evolution kinetics, endowing the iridium catalyst with a bifunctional activity for acidic overall water splitting with a total voltage of only 1.554 V at a current density of 10 mA cm-2. In light of the remarkable boundary-enhanced catalysis effects, the semicrystalline material should be further developed for other applications.

Understanding the Aging Mechanism of Na-Based Layered Oxide Cathodes with Different Stacking Structures.

Manganese-based layered oxides are one of the most promising cathodes for Na-ion batteries, but the prospect of their practical application is challenged by high sensitivity to ambient air. The stacking structure of materials is critical to the aging mechanism between layered oxides and air, but there remains a lack of systematic study. Herein, comprehensive research on model materials P-type Na0.50MnO2 and O-type Na0.85MnO2 reveals that the O-phase displays a much higher dynamic affinity toward moisture air compared to P-type compounds. For air-exposed O-type material, Na+ ions are extracted from the crystal lattice to form alkaline species at the surface in contact with air, accompanying by the increase of the valence state of transition metals. The series of undesired reactions result in an increase of interfacial resistance and huge capacity loss. Comparatively, the insertion of H2O into the Na layer is the main reaction during air-exposure of P-type material, and the inserted H2O can be extracted by high-temperature treatment. The H2O de/insertion process not only causes no performance degradation but also can enlarge the interlayer distance. With these understandings, we further propose a washing-resintering strategy to recover the performance of aged O-type materials and an aging strategy to build high-performance P-type materials.

Strategies for Electrochemically Sustainable H2 Production in Acid.

Acidified water electrolysis with fast kinetics is widely regarded as a promising option for producing H2 . The main challenge of this technique is the difficulty in realizing sustainable H2 production (SHP) because of the poor stability of most electrode catalysts, especially on the anode side, under strongly acidic and highly polarized electrochemical environments, which leads to surface corrosion and performance degradation. Research efforts focused on tuning the atomic/nano structures of catalysts have been made to address this stability issue, with only limited effectiveness because of inevitable catalyst degradation. A systems approach considering reaction types and system configurations/operations may provide innovative viewpoints and strategies for SHP, although these aspects have been overlooked thus far. This review provides an overview of acidified water electrolysis for systematic investigations of these aspects to achieve SHP. First, the fundamental principles of SHP are discussed. Then, recent advances on design of stable electrode materials are examined, and several new strategies for SHP are proposed, including fabrication of symmetrical heterogeneous electrolysis system and fluid homogeneous electrolysis system, as well as decoupling/hybrid-governed sustainability. Finally, remaining challenges and corresponding opportunities are outlined to stimulate endeavors toward the development of advanced acidified water electrolysis techniques for SHP.

In situ surface reduction for accessing atomically dispersed platinum on carbon sheets for acidic hydrogen evolution.

Exploring the simple yet well-controlled synthesis of atomically dispersed Pt catalysts is a crucial endeavour for harvesting clean hydrogen via the kinetics-favoured acidic electrochemical water splitting technique. Here we employed the use of defective carbon sheets by KOH etching as a substrate for the in situ surface reduction of Pt(IV) ions to prepare atomically dispersed Pt. Physical and electrochemical characterizations reveal a strong interaction between the carbon substrate and Pt species, providing the basis for the in situ surface reduction. The atomically dispersed Pt electrocatalyst exhibited high HER performance in a sulfuric acid electrolyte, with an overpotential as low as 55 mV at a current density of 100 mA cm-a, and better catalytic durability compared to the commercial Pt/C. The mechanism study revealed that the full utilization of atomically dispersed Pt and the optimized catalyst surface may enhance the recombination of adsorbed *H via the Volmer-Tafel mechanism to produce H2 at a high efficiency. In the light of high activity, durability, and low cost, the atomically dispersed Pt material is promising for acidic HER application.

Electrochemical CO2 Reduction on Cu: Synthesis-Controlled Structure Preference and Selectivity.

The electrochemical CO2 reduction reaction (ECO2 RR) on Cu catalysts affords high-value-added products and is therefore of great practical significance. The outcome and kinetics of ECO2 RR remain insufficient, requiring essentially the optimized structure design for the employed Cu catalyst, and also the fine synthesis controls. Herein, synthesis-controlled structure preferences and the modulation of intermediate's interactions are considered to provide synthesis-related insights on the design of Cu catalysts for selective ECO2 RR. First, the origin of ECO2 RR intermediate-dominated selectivity is described. Advanced structural engineering approaches, involving alloy/compound formation, doping/defect introduction, and the use of specific crystal facets/amorphization, heterostructures, single-atom catalysts, surface modification, and nano-/microstructures, are then reviewed. In particular, these structural engineering approaches are discussed in association with diversified synthesis controls, and the modulation of intermediate generation, adsorption, reaction, and additional effects. The results pertaining to synthetic methodology-controlled structural preferences and the correspondingly motivated selectivity are further summarized. Finally, the current opportunities and challenges of Cu catalyst fabrication for highly selective ECO2 RR are discussed.

Stepwise chemical oxidation to access ultrathin metal (oxy)-hydroxide nanosheets for the oxygen evolution reaction.

Incorporation of ultrathin nanosheets with dopants/defects shows great potential to enable metal (oxy)-hydroxide electrocatalysts with enhanced oxygen evolution reaction (OER) performance via the regulation of atomic structure and bonding arrangements. However, it remains challenging in synthesis especially for such dual control and at large scale. In this study, we present a stepwise chemical oxidation route, involving phase transition and reconstruction processes, to access ultrathin CoOOH nanosheets with a thickness of ca. 4 nm and abundant oxygen vacancies. Other transition metals were also doped into CoOOH nanosheets through this strategy. Among them, the optimized FeCoOOH nanosheets demonstrated an efficient OER activity with overpotential as low as 252 mV (current density: 10 mA cm-2) and excellent stability. A high and stable solar-to-hydrogen efficiency of 10.5% was acquired when FeCoOOH nanosheets were used as the anode in a constructed water splitting device driven by solar energy. This study offers a noble and facile strategy for potentially scalable preparation of atom-modulated ultrathin metal (oxy)-hydroxide nanosheets, and also demonstrates the OER applications.

Reversible Hybrid Aqueous Li-CO2 Batteries with High Energy Density and Formic Acid Production.

Metal-CO2 batteries, an attractive technology for both energy storage and CO2 utilization, are typically classified into organic Li(Na)-CO2 batteries with a high energy density/output voltage and aqueous Zn-CO2 batteries with flexible chemical production. However, achieving both high-efficiency energy storage and flexible chemical production is still challenging. In this study, a reversible hybrid aqueous Li-CO2 battery is developed, integrating Li with an aqueous phase, which exhibits not only a high operating voltage and energy density but also highly selective formic acid production. Based on a Li plate as the anode, NaCl solution as the aqueous electrolyte, solid electrolyte Li1.5 Al0.5 Ge1.5 P3 O12 (LAGP) as a separator and Li+ transporter, and a bifunctional Pd-based electrocatalyst as the cathode, the resulting battery shows a high discharge voltage of up to 2.6 V, an outstanding energy conversion efficiency of above 80 %, and remarkable selectivity of CO2 -to-HCOOH conversion of up to 97 %. The related reaction mechanism is proposed as CO2 +2 Li+2 H+ ⇌HCOOH+2 Li+ .

Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction.

Ammonia (NH3) is a pivotal precursor in fertilizer production and a potential energy carrier. Currently, ammonia production worldwide relies on the traditional Haber-Bosch process, which consumes massive energy and has a large carbon footprint. Recently, electrochemical dinitrogen reduction to ammonia under ambient conditions has attracted considerable interest owing to its advantages of flexibility and environmental friendliness. However, the biggest challenge in dinitrogen electroreduction, i.e., the low efficiency and selectivity caused by poor specificity of electrocatalysts/electrolytic systems, still needs to be overcome. Although substantial progress has been made in recent years, acquiring most available electrocatalysts still relies on low efficiency trial-and-error methods. It is thus imperative to establish some critical guiding principles for nitrogen electroreduction toward a rational design and accelerated development of this field. Herein, a basic understanding of dinitrogen electroreduction processes and the inherent relationships between adsorbates and catalysts from fundamental theory are described, followed by an outline of the crucial principles for designing efficient electrocatalysts/electrocatalytic systems derived from a systematic evaluation of the latest significant achievements. Finally, the future research directions and prospects of this field are given, with a special emphasis on the opportunities available by following the guiding principles.

Rechargeable Zn-CO2 Electrochemical Cells Mimicking Two-Step Photosynthesis.

Metal-CO2 batteries represent a promising priority for sustainable energy and the environment. However, CO2 utilization in nonaqueous electrolytes mostly involves difficult CO2 electrochemistry, leading to poor selectivity and limited cycle performance. Herein, an aqueous rechargeable Zn-CO2 electrochemical cell that tunably produced CO fuel gas (90% Faradaic efficiency) during cell discharge (cathodic reaction: CO2 + 2e- + 2H+ → CO + H2 O) and O2 during cell charge at ≈2 V (cathodic reaction: H2 O → 1/2O2 + 2e- + 2H+ ), mimicking the separate steps of CO2 fixation and water oxidation during photosynthesis while exhibiting the advantages of high efficiency, tunable products, and operation independent of sunlight is proposed and realized. The cell achieves a remarkable energy efficiency of 68% with fuel generation, providing an alternative for the green, efficient, and safe utilization of CO2 by metal-CO2 batteries.

Atomic Modulation and Structure Design of Carbons for Bifunctional Electrocatalysis in Metal-Air Batteries.

With the extensive research and development of renewable energy technologies, there is an increasing interest in developing metal-free carbons as a new class of bifunctional electrocatalysts for boosting the performance of metal-air batteries. Along with significant understanding of the electrocatalytic nature and the rapid development of techniques, the activities of carbon electrocatalysts are well-tailored by introducing particular dopants/defects and structure regulation. Herein, the recent advances regarding the rational design of carbon-based electrocatalysts for the oxygen reduction reaction and oxygen evolution reaction are summarized, with a special focus on the bifunctional applications in Zn-air and Li-air batteries. Specifically, the atomic modulation strategies to regulate the electrocatalytic activities of carbons and structure modification are summarized to gain deep insights into bifunctional mechanisms and boost advanced Zn-air and Li-air batteries. The current challenges and future perspectives are also addressed to accelerate the exploration of promising bifunctional carbon catalysts for renewable energy technologies, particularly metal-air batteries.

Reversible Aqueous Zinc-CO2 Batteries Based on CO2 -HCOOH Interconversion.

As a promising technique for CO2 fixation/utilization and energy conversion/storage, the metal-CO2 battery has been studied to improve its interconversion between CO2 and carbonates/oxalates. Herein, we propose and realize a reversible aqueous Zn-CO2 battery based on the reversible conversion between CO2 and liquid HCOOH on a bifunctional Pd cathode. The 3D porous Pd interconnected nanosheet with enriched edge and pore structure, has a highly electrochemical active surface to facilitate simultaneous selective CO2 reduction and HCOOH oxidation at low overpotentials. The resulting battery has a 1 V charge voltage, a cycling durability over 100 cycles, and a high energy efficiency of 81.2 %. The battery mechanism is proposed as Zn+CO2 +2 H+ +2 OH- ↔ ZnO+HCOOH+H2 O, through which the reversible conversion between CO2 and liquid HCOOH was realized.

Mixed-Metal-Organic Framework Self-Template Synthesis of Porous Hybrid Oxyphosphides for Efficient Oxygen Evolution Reaction.

Developing an efficient, stable yet cost-effective electrocatalyst is the key link along the path to hydrogen fuels produced by water splitting. The current bottleneck in the water electrolysis technology is the sluggish oxygen-evolving reaction (OER) which is also central to the rechargeable metal-air batteries. Herein, we report a promising mixed-metal-organic framework (MMOF) self-template strategy to synthesize CoFe hybrid oxyphosphides with highly porous morphology. Aided by the porous hybrid bulk structure beneficial to fast-ion diffusion to abundant highly active sites, the as-synthesized Co3FePxO exhibited excellent electrocatalytic activity toward OER, with an overpotential of 291 mV at 10 mA cm-2 and a low Tafel slope of 85 mV dec-1. With the underpinnings of MMOF maintaining the structural rigidity and stability, the material also showed long life for OER without  discernible activity decay.

Highly exposed Fe-N4 active sites in porous poly-iron-phthalocyanine based oxygen reduction electrocatalyst with ultrahigh performance for air cathode.

Progress in the development of efficient electrocatalysts for oxygen reduction reactions is imperative for various energy systems such as metal-air batteries and fuel cells. In this paper, an innovative porous two-dimensional (2D) poly-iron-phthalocyanine (PFe-Pc) based oxygen reduction electrocatalyst created with a simple solid-state chemical reaction without pyrolysis is reported. In this strategy, silicon dioxide nanoparticles play a pivotal role in preserving the Fe-N4 structure during the polymerization process and thereby assist in the development of a porous structure. The new polymerized phthalocyanine electrocatalyst with tuned porous structure, improved specific surface area and more exposed catalytic active sites via the 2D structure shows an excellent performance towards an oxygen reduction reaction in alkaline media. The onset potential (E = 1.033 V) and limiting current density (I = 5.58 mA cm-2) are much better than those obtained with the commercial 20% platinum/carbon electrocatalyst (1.046 V and 4.89 mA cm-2) and also show better stability and tolerance to methanol crossover. For practical applications, a zinc-air (Zn-air) battery and methanol fuel cell equipped with the PFe-Pc electrocatalyst as an air cathode reveal a high open circuit voltage and maximum power output (1.0 V and 23.6 mW cm-2 for a methanol fuel cell, and 1.6 V and 192 mW cm-2 for the liquid Zn-air battery). In addition, using the PFe-Pc electrocatalyst as an air cathode in a flexible cable-type Zn-air battery exhibits excellent performance with an open-circuit voltage of 1.409 V. This novel porous 2D PFe-Pc has been designed logically using a new, simple strategy with ultrahigh electrochemical performances in Zn-air batteries and methanol fuel cell applications.

Multisource Synergistic Electrocatalytic Oxidation Effect of Strongly Coupled PdM (M = Sn, Pb)/N-doped Graphene Nanocomposite on Small Organic Molecules.

A series of palladium-based catalysts of metal alloying (Sn, Pb) and/or (N-doped) graphene support with regular enhanced electrocatalytic activity were investigated. The peak current density (118.05 mA cm(-2)) of PdSn/NG is higher than the sum current density (45.63 + 47.59 mA cm(-2)) of Pd/NG and PdSn/G. It reveals a synergistic electrocatalytic oxidation effect in PdSn/N-doped graphene Nanocomposite. Extend experiments show this multisource synergetic catalytic effect of metal alloying and N-doped graphene support in one catalyst on small organic molecule (methanol, ethanol and Ethylene glycol) oxidation is universal in PdM(M = Sn, Pb)/NG catalysts. Further, The high dispersion of small nanoparticles, the altered electron structure and Pd(0)/Pd(II) ratio of Pd in catalysts induced by strong coupled the metal alloying and N-doped graphene are responsible for the multisource synergistic catalytic effect in PdM(M = Sn, Pb) /NG catalysts. Finally, the catalytic durability and stability are also greatly improved.