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Hydrogen is a clean and renewable energy carrier for powering future transportation and other applications. Water electrolysis is a promising option for hydrogen production from renewable resources such as wind and solar energy. To date, tremendous efforts have been devoted to the development of electrocatalysts and membranes for water electrolysis technology. In principle, water electrolysis in acidic media has several advantages over that in alkaline media, including favorable reaction kinetics, easy product separation, and low operating pressure. However, acidic water electrolysis poses higher requirements for the catalysts, especially the ones for the oxygen evolution reaction. It is a grand challenge to develop highly active, durable, and cost‐effective catalysts to replace precious metal catalysts for acidic water oxidation. In this article, an overview is presented of the latest developments in design and synthesis of electrocatalysts for acidic water oxidation, emphasizing new strategies for achieving high electrocatalytic activity while maintaining excellent durability at low cost. In particular, the reaction pathways and intermediates are discussed in detail to gain deeper insight into the oxygen evolution reaction mechanism, which is vital to rational design of more efficient electrocatalysts. Further, the remaining scientific challenges and possible strategies to overcome them are outlined, together with perspectives for future‐generation electrocatalysts that exploit nanoscale materials for water electrolysis. [ABSTRACT FROM AUTHOR]

Nanostructured molybdenum disulfide (MoS2) has been arousing great research interest in many fields in recent years due to their peculiar properties. In this short review, we introduce recent advances in nanostructured MoS2 as potential materials for construction of electrochemical sensors. The potential application prospect of the electrochemical sensors based on MoS2 nanomaterials is proposed. [ABSTRACT FROM AUTHOR]

MoS2 nanoparticles supported on gold nanoparticle films (AuNP/MoS2 films) were constructed by a simple two-step drop-casting modification process on a glassy carbon electrode. The films realized a direct four-electron pathway for the oxygen reduction reaction (ORR) in alkaline media with an onset potential of −0.10 V versus the saturated calomel electrode. The films exhibited superior stability and better electrocatalytic performance than commercial Pt/C. Electrochemical studies and composition characterization illustrated that the enhanced catalytic activity of the AuNP/MoS2 films could be attributed to the synergistic effect of the positive onset potential of the gold nanoparticles for the ORR and the four-electron oxygen reduction properties of the ultrasmall MoS2 nanoparticles, which is different from gold nanoparticle and MoS2 nanoparticle modified electrodes. [ABSTRACT FROM AUTHOR]

Full(erene) of surprises: The first isomerically pure multi‐hydroxylated fullerene, C60(OH)8, shows a reduction peak and a reoxidation peak in aqueous solution. With surprising catalytic performance in the hydrogen evolution reaction (HER), when electrodeposited on a glassy carbon electrode (GCE), salts of C60(OH)8 may prove to be effective molecular catalysts for conducting the HER without transition metals. [ABSTRACT FROM AUTHOR]

O ‐ H ‐ Erlebnis: Das erste isomerenreine mehrfach hydroxylierte Fulleren, C60(OH)8, lässt sich in wässriger Lösung oxidieren und reduzieren. Ein elektrochemisch auf einer Glaskohlenstoffelektrode (GCE) abgeschiedenes C60(OH)8 ‐ Salz ist ein überraschend aktiver übergangsmetallfreier Katalysator der Wasserstoffentwicklung. [ABSTRACT FROM AUTHOR]

MoS2 particles with different size distributions were prepared by simple ultrasonication of bulk MoS2 followed by gradient centrifugation. Relative to the inert microscale MoS2, nanoscale MoS2 showed significantly improved catalytic activity toward the oxygen-reduction reaction (ORR) and hydrogen-evolution reaction (HER). The decrease in particle size was accompanied by an increase in catalytic activity. Particles with a size of around 2 nm exhibited the best dual ORR and HER performance with a four-electron ORR process and an HER onset potential of −0.16 V versus the standard hydrogen electrode (SHE). This is the first investigation on the size-dependent effect of the ORR activity of MoS2, and a four-electron transfer route was found. The exposed abundant Mo edges of the MoS2 nanoparticles were proven to be responsible for the high ORR catalytic activity, whereas the origin of the improved HER activity of the nanoparticles was attributed to the plentiful exposed S edges. This newly discovered process provides a simple protocol to produce inexpensive highly active MoS2 catalysts that could easily be scaled up. Hence, it opens up possibilities for wide applications of MoS2 nanoparticles in the fields of energy conversion and storage. [ABSTRACT FROM AUTHOR]

Abstract: Aiming to improve the charge transfer ability at the neural electrode interface, a new and simple method for amino-functionalization of carbon nanotubes (CNTs) has been attempted, and the amino-functionalized CNTs after quaternization were electrodeposited onto pretreated Pt microelectrodes using an 80V cell voltage in anhydrous solvent. The formation of amino-functionalized CNTs and electrodeposition of the functionalized CNTs were confirmed by Fourier transform infrared (FT-IR) spectroscopy and SEM images respectively. The deposited electrodes exhibited a reduction by 91% in the electrode impedance at 1kHz compared to smooth Pt electrodes. In addition, the CNT deposited electrodes possessed a large charge storage capacity, and provided an increased safe charge injection (Qinj ) limit (1.6–2.0mC/cm2) that is ten times higher than that of Pt electrodes. Electrochemical stability is another important characteristic required by neural electrodes. It was found that the CNT deposited microelectrodes were very stable during electrical stimulation, which is highly desirable for implantable neural electrodes. In summary, this study developed an easy and mild coating method for elevating the safe charge injection limit of neural microelectrodes, which can be applied to neural prostheses such as visual prostheses. [Copyright &y& Elsevier]

Abstract: An efficient and reliable electrochemical method for preparing electrodeposited iridium oxide film (EIROF) microelectrodes by an anodic electrochemical process is reported. The EIROF microelectrodes exhibited remarkably high safe charge injection (Q inj) limits of ∼2.6mC/cm2 for anodic-first pulses and ∼1.4mC/cm2 for cathodic-first pulses, and the electrode impedance at 1kHz was significantly reduced by ∼92%. The EIROF microelectrodes also exhibited good mechanical and electrochemical stability, as well as an excellent super-Nernstian slope in a broad pH range (1–13). All of these characteristics are greatly desired for neural sensor applications including electrical neural microstimulation, neural signal recording as well as pH monitoring in vivo. Moreover, the electrodepositing method can be facilely incorporated into thin-film technology and Microelectromechanical Systems (MEMS). [Copyright &y& Elsevier]

Developing efficient and anti‐corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal‐support interaction (RMSI) as ORR catalysts, using Ni‐doped cubic ZrO2 (Ni/ZrO2) supported L10−PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt. The optimal L10−PtNi−Ni/ZrO2−RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8 %) after 400,000 accelerated durability test cycles in a half‐cell and exceptional PEMFC performance (MA=0.76 A mgPt−1 at 0.9 V, peak power density=1.52/0.92 W cm−2 in H2−O2/−air, and 18.4 % MA decay after 30,000 cycles), representing the best reported Pt‐based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10−PtNi−Ni/ZrO2−RMSI requires a lower energetic barrier for ORR than L10−PtNi−Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10−PtNi−Ni/ZrO2−RMSI compared to L10−PtNi−C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy. [ABSTRACT FROM AUTHOR]

Developing efficient and anti‐corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal‐support interaction (RMSI) as ORR catalysts, using Ni‐doped cubic ZrO2 (Ni/ZrO2) supported L10−PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt. The optimal L10−PtNi−Ni/ZrO2−RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8 %) after 400,000 accelerated durability test cycles in a half‐cell and exceptional PEMFC performance (MA=0.76 A mgPt−1 at 0.9 V, peak power density=1.52/0.92 W cm−2 in H2−O2/−air, and 18.4 % MA decay after 30,000 cycles), representing the best reported Pt‐based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10−PtNi−Ni/ZrO2−RMSI requires a lower energetic barrier for ORR than L10−PtNi−Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10−PtNi−Ni/ZrO2−RMSI compared to L10−PtNi−C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy. [ABSTRACT FROM AUTHOR]

Engineering the crystal structure of Pt–M (M = transition metal) nanoalloys to chemically ordered ones has drawn increasing attention in oxygen reduction reaction (ORR) electrocatalysis due to their high resistance against M etching in acid. Although Pt–Ni alloy nanoparticles (NPs) have demonstrated respectable initial ORR activity in acid, their stability remains a big challenge due to the fast etching of Ni. In this work, sub‐6 nm monodisperse chemically ordered L10‐Pt–Ni–Co NPs are synthesized for the first time by employing a bifunctional core/shell Pt/NiCoOx precursor, which could provide abundant O‐vacancies for facilitated Pt/Ni/Co atom diffusion and prevent NP sintering during thermal annealing. Further, Co doping is found to remarkably enhance the ferromagnetism (room temperature coercivity reaching 2.1 kOe) and the consequent chemical ordering of L10‐Pt–Ni NPs. As a result, the best‐performing carbon supported L10‐PtNi0.8Co0.2 catalyst reveals a half‐wave potential (E1/2) of 0.951 V versus reversible hydrogen electrode in 0.1 m HClO4 with 23‐times enhancement in mass activity over the commercial Pt/C catalyst along with much improved stability. Density functional theory (DFT) calculations suggest that the L10‐PtNi0.8Co0.2 core could tune the surface strain of the Pt shell toward optimized Pt–O binding energy and facilitated reaction rate, thereby improving the ORR electrocatalysis. [ABSTRACT FROM AUTHOR]

The harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt‐based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10−Pt2CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt−Ga as high‐performance PEMFC cathode catalysts. The L10−Pt2CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt−1 at 0.9 V, peak power density=2.60/1.24 W cm−2 in H2‐O2/air, 28 mV voltage loss at 0.8 A cm−2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10−Pt2CuGa surface, and the durability enhancement stems from the stronger Pt−M bonds than those in L11−PtCu resulted from Pt−Ga covalent interactions. [ABSTRACT FROM AUTHOR]

The harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt‐based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10−Pt2CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt−Ga as high‐performance PEMFC cathode catalysts. The L10−Pt2CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt−1 at 0.9 V, peak power density=2.60/1.24 W cm−2 in H2‐O2/air, 28 mV voltage loss at 0.8 A cm−2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10−Pt2CuGa surface, and the durability enhancement stems from the stronger Pt−M bonds than those in L11−PtCu resulted from Pt−Ga covalent interactions. [ABSTRACT FROM AUTHOR]

Abstract Prussian blue analogues (PBAs) with open frameworks have drawn much attention in energy storage fields due to their tridimensional ionic diffusion path, easy preparation, and low cost. This review summarizes the recent progress of using PBAs and their derivatives as energy storage materials in alkali ions, multi-valent ions, and metal-air batteries. The key factors to improve the electrochemical performance of PBAs as cathode materials in rechargeable batteries were firstly discussed. Several approaches for performance enhancement such as controlling the amounts of vacancies and coordinated water, optimizing morphologies, and depositing carbon coating are described in details. Then, we highlighted the significance of their diverse architectures and morphologies in anode materials for lithium/sodium ion batteries. Finally, the applications of Prussian blue derivatives as catalysts in metal-air batteries are also reviewed, providing insights into the origin of favorable morphologies and structures of catalyst for the optimal performance. [ABSTRACT FROM AUTHOR]

Directly splitting seawater to produce hydrogen provides a promising pathway for energy and environmental sustainability. However, current seawater splitting faces many challenges because of the sluggish kinetics, the presence of impurities, membrane contamination, and the competitive chloride oxidation reaction at the anode, which makes it more difficult than freshwater splitting. This Review firstly introduces the basic mechanisms of the anode and cathode reactions during seawater splitting. We critically analyze the primary principles for designing catalysts for seawater splitting in terms of both the hydrogen and oxygen evolution reactions, including with noble metal, noble metal free, and metal‐free catalysts. Strategies to design effective catalysts, such as active site population, synergistic effect regulation, and surface engineering, are discussed. Furthermore, promises, perspectives, and challenges in developing seawater splitting technologies for clean hydrogen generation are summarized. [ABSTRACT FROM AUTHOR]

Directly splitting seawater to produce hydrogen provides a promising pathway for energy and environmental sustainability. However, current seawater splitting faces many challenges because of the sluggish kinetics, the presence of impurities, membrane contamination, and the competitive chloride oxidation reaction at the anode, which makes it more difficult than freshwater splitting. This Review firstly introduces the basic mechanisms of the anode and cathode reactions during seawater splitting. We critically analyze the primary principles for designing catalysts for seawater splitting in terms of both the hydrogen and oxygen evolution reactions, including with noble metal, noble metal free, and metal‐free catalysts. Strategies to design effective catalysts, such as active site population, synergistic effect regulation, and surface engineering, are discussed. Furthermore, promises, perspectives, and challenges in developing seawater splitting technologies for clean hydrogen generation are summarized. [ABSTRACT FROM AUTHOR]

Although Pd is a potential substitution of Pt‐based catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), the binding of *H and oxygenated (*O, *OOH, *OH) intermediates on Pd are stronger than on Pt, leading to its inferior activity for HER and ORR. In this work, CuPd/Pd core/shell nanoparticles with an ultrathin Pd shell (0.5 nm) are developed, which demonstrate the Pt‐like bifunctional activity for HER and ORR in acid electrolytes. The overpotential at 350 mA cm−2 for HER and the half‐wave potential for ORR on the optimal CuPd/Pd core/shell NPs are 76 mV and 0.854 V versus reversible hydrogen electrode (RHE), respectively, which are comparable to that of Pt and among the best of the reported Pd‐based catalysts. Density functional theory calculations indicate that the significantly enhanced HER/ORR activity on CuPd/Pd core/shell NPs with 0.5 nm Pd shell stem from the compressive strain induced downshift of d‐band center for Pd (by 2.0%), which weakens the binding strength of *H and oxygenated intermediates and promotes the reaction kinetics. [ABSTRACT FROM AUTHOR]

The electrochemical CO2 reduction reaction (CO2RR) to form highly valued chemicals is a sustainable solution to address the environmental issues caused by excessive CO2 emissions. Generally, it is challenging to achieve high efficiency and selectivity simultaneously in the CO2RR due to multi-proton/electron transfer processes and complex reaction intermediates. Among the studied formulations, bimetallic catalysts have attracted significant attention with promising activity, selectivity, and stability. Engineering the atomic arrangement of bimetallic nanocatalysts is a promising strategy for the rational design of structures (intermetallic, core/shell, and phase-separated structures) to improve catalytic performance. This review summarizes the recent advances, challenges, and opportunities in developing bimetallic catalysts for the CO2RR. In particular, we firstly introduce the possible reaction pathways on bimetallic catalysts concerning the geometric and electronic properties of intermetallic, core/shell, and phase-separated structures at the atomic level. Then, we critically examine recent advances in crystalline structure engineering for bimetallic catalysts, aiming to establish the correlations between structures and catalytic properties. Finally, we provide a perspective on future research directions, emphasizing current challenges and opportunities. [ABSTRACT FROM AUTHOR]

PtM alloy catalysts (e.g., PtFe, PtCo), especially in an intermetallic L10 structure, have attracted considerable interest due to their respectable activity and stability for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, metal‐catalyzed formation of ·OH from H2O2 (i.e., Fenton reaction) by Fe‐ or Co‐containing catalysts causes severe degradation of PEM/catalyst layers, hindering the prospects of commercial applications. Zinc is known as an antioxidant in Fenton reaction, but is rarely alloyed with Pt owing to its relatively negative redox potential. Here, sub‐4 nm intermetallic L10‐PtZn nanoparticles (NPs) are synthesized as high‐performance PEMFC cathode catalysts. In PEMFC tests, the L10‐PtZn cathode achieves outstanding activity (0.52 A mgPt−1 at 0.9 ViR‐free, and peak power density of 2.00 W cm−2) and stability (only 16.6% loss in mass activity after 30 000 voltage cycles), exceeding the U.S. DOE 2020 targets and most of the reported ORR catalysts. Density function theory calculations reveal that biaxial strains developed upon the disorder‐order (A1L10) transition of PtZn NPs would modulate the surface PtPt distances and optimize PtO binding for ORR activity enhancement, while the increased vacancy formation energy of Zn atoms in an ordered structure accounts for the improved stability. [ABSTRACT FROM AUTHOR]

The commercialization of proton exchange membrane fuel cells (PEMFCs) relies on highly active and stable electrocatalysts for oxygen reduction reaction (ORR) in acid media. The most successful catalysts for this reaction are nanostructured Pt‐alloy with a Pt‐skin. The synthesis of ultrasmall and ordered L10‐PtCo nanoparticle ORR catalysts further doped with a few percent of metals (W, Ga, Zn) is reported. Compared to commercial Pt/C catalyst, the L10‐W‐PtCo/C catalyst shows significant improvement in both initial activity and high‐temperature stability. The L10‐W‐PtCo/C catalyst achieves high activity and stability in the PEMFC after 50 000 voltage cycles at 80 °C, which is superior to the DOE 2020 targets. EXAFS analysis and density functional theory calculations reveal that W doping not only stabilizes the ordered intermetallic structure, but also tunes the Pt‐Pt distances in such a way to optimize the binding energy between Pt and O intermediates on the surface. [ABSTRACT FROM AUTHOR]

The commercialization of proton exchange membrane fuel cells (PEMFCs) relies on highly active and stable electrocatalysts for oxygen reduction reaction (ORR) in acid media. The most successful catalysts for this reaction are nanostructured Pt‐alloy with a Pt‐skin. The synthesis of ultrasmall and ordered L10‐PtCo nanoparticle ORR catalysts further doped with a few percent of metals (W, Ga, Zn) is reported. Compared to commercial Pt/C catalyst, the L10‐W‐PtCo/C catalyst shows significant improvement in both initial activity and high‐temperature stability. The L10‐W‐PtCo/C catalyst achieves high activity and stability in the PEMFC after 50 000 voltage cycles at 80 °C, which is superior to the DOE 2020 targets. EXAFS analysis and density functional theory calculations reveal that W doping not only stabilizes the ordered intermetallic structure, but also tunes the Pt‐Pt distances in such a way to optimize the binding energy between Pt and O intermediates on the surface. [ABSTRACT FROM AUTHOR]

Abstract: The development of high‐performance oxygen reduction reaction (ORR) catalysts derived from non‐Pt group metals (non‐PGMs) is urgent for the wide applications of proton exchange membrane fuel cells (PEMFCs). In this work, a facile and cost‐efficient supramolecular route is developed for making non‐PGM ORR catalyst with atomically dispersed Fe‐Nx/C sites through pyrolyzing the metal‐organic polymer coordinative hydrogel formed between Fe3+ and α‐L‐guluronate blocks of sodium alginate (SA). High‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) and X‐ray absorption spectroscopy (XAS) verify that Fe atoms achieve atomic‐level dispersion on the obtained SA‐Fe‐N nanosheets and a possible fourfold coordination with N atoms. The best‐performing SA‐Fe‐N catalyst exhibits excellent ORR activity with half‐wave potential (E1/2) of 0.812 and 0.910 V versus the reversible hydrogen electrode (RHE) in 0.5 m H2SO4 and 0.1 m KOH, respectively, along with respectable durability. Such performance surpasses that of most reported non‐PGM ORR catalysts. Density functional theory calculations suggest that the relieved passivation effect of OH* on Fe‐N4/C structure leads to its superior ORR activity to Pt/C in alkaline solution. The work demonstrates a novel strategy for developing high‐performance non‐PGM ORR electrocatalysts with atomically dispersed and stable M‐Nx coordination sites in both acidic and alkaline media. [ABSTRACT FROM AUTHOR]

Tin selenide (SnSe) has been explored as a promising anode material for sodium ion batteries (SIBs) but its electrochemical performance is strictly limited by the large volume variation during charge/discharge process and relatively low electronic conductivity. In this work, hierarchical Cu doped SnSe nanoclusters were prepared by a cost-efficient and nontoxic method and demonstrated as a high-performance anode for SIBs. Under optimized Cu doping degree (10 wt% Cu), the developed Cu-SnSe anode exhibits excellent rate performance with a high capacity of 330 mAh/g at 20 A/g and outstanding stability with a capacity of 304 mAh/g after 1000 cycles at 5 A/g (0.1–3.0 V vs. Na/Na + ). The enhanced electronic conductivity, facilitated sodiation/desodiation process, and relieved volume change during cycling in Cu doped SnSe benefited from Cu doping and the unique hierarchical structure should account for its extraordinary sodiun storage performance. [ABSTRACT FROM AUTHOR]

The instinct scaling relations between the adsorption energies of key intermediates during OER lead to large overpotential for water/seawater splitting. Herein, we develop a new strategy to fabricate amorphous nickel-iron phosphides (NiFeP) with controllable morphologies as high-performance catalysts for overall seawater splitting. The ligand effect of P tunes the electronic states of the oxidized NiFe sites, thus breaks the scaling relations for OER and reduce the adsorption energy gap between HO* and HOO* from 3.08 eV to 2.62 eV. The NiFeP nanostructures exhibit extraordinarily low overpotentials of 129 mV for OER and 126 mV for HER at 100 mA cm−2 in simulated alkaline seawater, which outperform the best reported electrocatalysts. They could also be operated at 1.57 V with 100 mA cm−2 in a two-electrode electrolyzer and work for more than 500 h. Our work may provide a universal guidance for the design of highly active seawater splitting electrocatalysts. Amorphous NiFeP catalysts with extremely high activity for overall seawater splitting are developed. Theoretical calculations suggest that the P atom on the oxidized NiFe surface can significantly reduce the adsorption free energy gap between HO* and HOO*, thus breaks the scaling relations for oxygen evolution significantly and enhances the activity. The NiFeP catalysts can be operated for more than 500 h, demonstrating exceptional durability. [Display omitted] • Amorphous NiFeP with controllable morphologies were prepared as bifunctional catalysts for overall seawater splitting. • P on the oxidized NiFe surface can break the scaling relations for OER and reduce the energy barrier between HO* and HOO*. • P can optimize the adsorption/desorption of H* on the amorphous NiFe structure and facilitate the evolution of hydrogen. • The catalysts can operate at 1.57 V with a current density of 100 mA cm-2 in a two-electrode electrolyzer and work for 500 h. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bi-Pd single atom alloy (SAA) nanodendrites (NDs) with Bi atomically dispersed in Pd matrices have been synthesized. • The FEs of CO on Bi 6 Pd 94 -SAA NDs catalyst reach 90.5 % and 91.8 % in H-type and gas diffusion flow cells, respectively. • The Pd mass normalized current densities of CO are 173.7 mA/cm2 and 111.4 A/g Pd at only -0.48 vs. RHE in a gas diffusion flow cell. • DFT calculation indicate that single Bi atom doping decreases H affinity and increases the reaction barrier for H 2 evolution on Pd. • Bi doping also decreases the free energy for *COOH generation which is a key intermediate for CO production. Pd is a catalyst for electrochemical CO 2 reduction to CO but often disturbed by H 2 and formate formation at low overpotentials due to its strong affinity to H atoms. Herein, guided by density functional theory (DFT) calculations, Bi-Pd single atom alloy (SAA) nanodendrites (NDs) with Bi atomically dispersed in Pd matrices have been developed for efficient CO 2 reduction to CO. The Faradic efficiencies (FEs) of CO on the Bi 6 Pd 94 -SAA ND catalyst reach 90.5 % and 91.8 % in H-type and gas diffusion flow cells with overpotentials of only 290 and 200 mV, respectively, which are among the best of the reported Pd-based electrocatalysts. The greatly enhanced CO formation on the Bi 6 Pd 94 -SAA NDs can be attributed to the increased reaction barriers for H 2 formation due to a lower H coverage resulted from Bi doping, and the decreased free energy for *COOH generation which is a key intermediate for CO production. [ABSTRACT FROM AUTHOR]

Lithium-sulfur (Li–S) battery has aroused intensive attention due to its intrinsicly high capacity and energy density. However, the sluggish kinetics of lithium polysulfide (LiPS) redox conversion and shuttle effect severely damage the sulfur utilization, rate performance, and cycling stability of Li–S batteries. In this work, we report that Ru-doping induced phase transformation from MoP to Mo 4 P 3 (Ru–Mo 4 P 3) could significantly facilitate the electrocatalytic conversion of LiPS. When Ru–Mo 4 P 3 nanoparticles (NPs) are decorated on hollow carbon spheres (HCS), the S/HCS-Ru-Mo 4 P 3 electrode delivers high reversible capacities of 1178 mAh g−1 and 660 mAh g−1 at 0.5C and 4C in Li–S battery, respectively. The rate performance of the developed S/HCS-Ru-Mo 4 P 3 is among the best of the reported transition metal phosphide cathodes for Li–S batteries. When the S loading is as high as 6.6 mg cm−2, S/HCS-Ru-Mo 4 P 3 retains a reversible areal capacity of 5.6 mAh cm−2 after 50 cycles, higher than that of the commercial Li-ion battery (4 mAh cm−2). The excellent Li–S battery performance can be attributed to the intrinsically active Ru–Mo 4 P 3 phase combining with hollow carbon structure, which significantly facilitates the electrocatalytic conversion and entrapment of LiPS. Image 1 [ABSTRACT FROM AUTHOR]