Nb2AlC MAX Nanosheets Supported Ru Nanocrystals as Efficient Catalysts for Boosting pH-Universal Hydrogen Production.

MAX phase combines both ceramic and metallic properties, which exhibits widespread application prospects. 2D MAX nanosheets have more abundant surface-active sites, being anticipated to improve the performance of surface-related applications. Herein, for the first time, 2D Nb2AlC nanosheets (NSs) as novel supports anchored with Ru catalysts for overall water splitting are developed. The optimized catalyst of Ru@Nb2AlC NSs exhibit Pt-comparable kinetics and superior catalytic activity toward hydrogen evolution reaction (HER) (low overpotentials of 61 and 169 mV at 10 and 100 mA cm-2, respectively) with excellent durability (5000 cycles or 80 h) in alkaline media. In particular, Ru@Nb2AlC NSs achieve a mass activity of ≈4.8 times larger than the commercial Pt/C (20 wt.%) catalyst. The post-oxidation resultant catalyst of RuO2@Nb2AlC NSs also exhibit boosting HER and oxygen evolution reaction activities and ≈100% Faraday efficiency for overall water splitting with a cell voltage of 1.61 V to achieve 10 mA cm-2. Therefore, the novel category of 2D MAX supports anchored with Ru nanocrystals offers a novel strategy for designing a wide range of MAX-supported metal catalysts for the renewable energy field.

Efficient and Stable pH-Universal Water Electrolysis Catalyzed by N-Doped Hollow Carbon Confined RuIrOx Nanocrystals.

A facile strategy is developed to fabricate 3 nm RuIrOx nanocrystals anchored onto N-doped hollow carbon for highly efficient and pH-universal overall water splitting and alkaline seawater electrolysis. The designed catalyst exhibits much lower overpotential and superior stability than most previously reported Ru- and Ir-based electrocatalysts for hydrogen/oxygen evolution reactions. It also manifests excellent overall water splitting activities and maintains ≈100% Faradic efficiency with a cell voltage of 1.53, 1.51, and 1.54 V at 10 mA cm-2 for 140, 255, and 200 h in acid, alkaline, and alkaline seawater electrolytes, respectively. The excellent electrocatalytic performance can be attributed to solid bonding between RuIrOx and the hollow carbon skeleton, and effective electronic coupling between Ru and Ir, thus inducing its remarkable electrocatalytic activities and long-lasting stability.

Improving Alkaline Hydrogen Oxidation through Dynamic Lattice Hydrogen Migration in Pd@Pt Core-Shell Electrocatalysts.

Tracking the trajectory of hydrogen intermediates during hydrogen electro-catalysis is beneficial for designing synergetic multi-component catalysts with division of chemical labor. Herein, we demonstrate a novel dynamic lattice hydrogen (LH) migration mechanism that leads to two orders of magnitude increase in the alkaline hydrogen oxidation reaction (HOR) activity on Pd@Pt over pure Pd, even ≈31.8 times mass activity enhancement than commercial Pt. Specifically, the polarization-driven electrochemical hydrogenation process from Pd@Pt to PdHx @Pt by incorporating LH allows more surface vacancy Pt sites to increase the surface H coverage. The inverse dehydrogenation process makes PdHx as an H reservoir, providing LH migrates to the surface of Pt and participates in the HOR. Meanwhile, the formation of PdHx induces electronic effect, lowering the energy barrier of rate-determining Volmer step, thus resulting in the HOR kinetics on Pd@Pt being proportional to the LH concentration in the in situ formed PdHx @Pt. Moreover, this dynamic catalysis mechanism would open up the catalysts scope for hydrogen electro-catalysis.

Recent Advances in Co-Based Electrocatalysts for Hydrogen Evolution Reaction.

Water splitting is a promising technique in the sustainable "green hydrogen" generation to meet energy demands of modern society. Its industrial application is heavily dependent on the development of novel catalysts with high performance and low cost for hydrogen evolution reaction (HER). As a typical non-precious metal, cobalt-based catalysts have gained tremendous attention in recent years and shown a great prospect of commercialization. However, the complexity of the composition and structure of newly-developed Co-based catalysts make it urgent to comprehensively retrospect and summarize their advance and design strategies. Hence, in this review, the reaction mechanism of HER is first introduced and the possible role of the Co component during electrocatalysis is discussed. Then, various design strategies that could effectively enhance the intrinsic activity are summarized, including surface vacancy engineering, heteroatom doping, phase engineering, facet regulation, heterostructure construction, and the support effect. The recent progress of the advanced Co-based HER electrocatalysts is discussed, emphasizing that the application of the above design strategies can significantly improve performance by regulating the electronic structure and optimizing the binding energy to the crucial intermediates. At last, the prospects and challenges of Co-based catalysts are shown according to the viewpoint from fundamental explorations to industrial applications.

Metal Phosphorous Chalcogenide: A Promising Material for Advanced Energy Storage Systems.

The development of efficient and affordable electrode materials is crucial for clean energy storage systems, which are considered a promising strategy for addressing energy crises and environmental issues. Metal phosphorous chalcogenides (MPX3 ) are a fascinating class of two-dimensional materials with a tunable layered structure and high ion conductivity, making them particularly attractive for energy storage applications. This review article aims to comprehensively summarize the latest research progress on MPX3 materials, with a focus on their preparation methods and modulation strategies. Additionally, the diverse applications of these novel materials in alkali metal ion batteries, metal-air batteries, and all-solid-state batteries are highlighted. Finally, the challenges and opportunities of MPX3 materials are presented to inspire their better potential in energy storage applications. This review provides valuable insights into the promising future of MPX3 materials in clean energy storage systems.

High-Valent Ni Species Induced by Inactive MoO2 for Efficient Urea Oxidation Reaction.

The microenvironment tuning of Ni species, a promising non-precious catalyst, is significant in the energy and environmentally relevant urea electro-oxidation reaction (UOR). Herein, we found that the high-valent Ni species induced by the inactive MoO2 in mixed nanocrystals of NiO/MoO2 were effective for urea oxidation. The redox interaction of MoO2 and NiO revealed by the spectroscopic analysis well supported the formation of high-valent Ni species and the changes in the surface chemical state. High catalytic activity and stability for urea oxidation were observed by a series of electrochemical measures compared to the counterpart catalysts of MoO2 and NiO. The optimal NiO/MoO2 hybrid catalyst showed a UOR activity of 73.1 mA cm-2 at 1.50 V, which was about 12-fold that of the NiO catalyst. In addition, largely improved catalytic kinetics and catalytic stability for UOR were also demonstrated. Because of the inactive activity of MoO2 and the low performance of NiO, the largely improved preference can be affirmatively attributed to the efficient catalytic synergism of NiO/MoO2 in the mixed nanocrystals. The current finding clarifies the catalytic promotion effect of the inactive Mo species on Ni-based catalysts for urea oxidation, which would be instructive for Ni/Mo-relevant catalyst development.

Depth probing of the hydride formation process in thin Pd films by combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy.

We demonstrate a flexible combined electrochemistry and fiber optics-based in situ UV/vis spectroscopy setup to gain insight into the depth evolution of electrochemical hydride and oxide formation in Pd films with thicknesses of 20 and 100 nm. The thicknesses of our model systems are chosen such that the films are thinner or significantly thicker than the optical skin depth of Pd to create two distinctly different situations. Low power white light is irradiated on the sample and analyzed in three different configurations; transmittance through, and, reflectance from the front and the back side of the film. The obtained optical sensitivities correspond to fractions of a monolayer of adsorbed or absorbed hydrogen (H) and oxygen (O) on Pd. Moreover, a combined simultaneous readout obtained from the different optical measurement configurations provides mechanistic insights into the depth-evolution of the studied hydrogenation and oxidation processes.

Widely available active sites on Ni2P for electrochemical hydrogen evolution--insights from first principles calculations.

We present insights into the mechanism and the active site for hydrogen evolution on nickel phosphide (Ni2P). Ni2P was recently discovered to be a very active non-precious hydrogen evolution catalyst. Current literature attributes the activity of Ni2P to a particular site on the (0001) facet. In the present study, using Density Functional Theory (DFT) calculations, we show that several widely available low index crystal facets on Ni2P have better properties for a high catalytic activity. DFT calculations were used to identify moderately bonding nickel bridge sites and nickel hollow sites for hydrogen adsorption and to calculate barriers for the Tafel pathway. The investigated surfaces in this study were the (101̅0), (1̅1̅20), (112̅0), (112̅1) and (0001) facets of the hexagonal Ni2P crystal. In addition to the DFT results, we present experiments on Ni2P nanowires growing along the 〈0001〉 direction, which are shown as efficient hydrogen evolution catalysts. The experimental results add these nanowires to a variety of different morphologies of Ni2P, which are all active for HER.

Easily-prepared dinickel phosphide (Ni2P) nanoparticles as an efficient and robust electrocatalyst for hydrogen evolution.

Polydispersed dinickel phosphide (Ni2P) nanoparticles were synthesized by a simple and scalable solid-state reaction. These nanoparticles are an excellent and robust catalyst for the electrochemical hydrogen evolution reaction, operating in both acidic and basic solutions.

An effective Pd-Ni(2)P/C anode catalyst for direct formic acid fuel cells.

The direct formic acid fuel cell is an emerging energy conversion device for which palladium is considered as the state-of-the-art anode catalyst. In this communication, we show that the activity and stability of palladium for formic acid oxidation can be significantly enhanced using nickel phosphide (Ni(2)P) nanoparticles as a cocatalyst. X-ray photoelectron spectroscopy (XPS) reveals a strong electronic interaction between Ni(2)P and Pd. A direct formic acid fuel cell incorporating the best Pd­Ni(2)P anode catalyst exhibits a power density of 550 mWcm(-2), which is 3.5 times of that of an analogous device using a commercial Pd anode catalyst.

Enhanced formic acid electrolysis of Pd sites by improved OH adsorption assisted by MoP.

MoP nanofiber-coupled Pd nanoparticles were demonstrated as efficient catalysts for formic acid-assisted water splitting in hydrogen generation. The theoretical calculations indicated that the OH on the surface of MoP through d-p bonding promoted the oxidation of CO at the Pd sites, and improved the ability to resist CO poisoning. As a result, enhanced catalytic performance was indicated.

Bi2Te3 nanosheets promoted Pd for ethylene glycol electrooxidation both in the dark and under visible light irradiation.

Ethylene glycol electrooxidation catalyzed by Pd nanoparticles was found to be largely improved by Bi2Te3 nanosheets both in the dark and under visible light irradiation.

An active Ni(OH)2/MnCO3 catalyst with efficient synergism for alkaline methanol oxidation.

A novel Ni(OH)2/MnCO3 hybrid catalyst was developed for high-performing alkaline methanol electro-oxidation, which could well overcome the shortages of inactive MnCO3 and low intrinsic Ni(OH)2 due to the good synergistic catalysis effect from the Jahn-Teller distortion effect.

Alleviating the competitive adsorption of hydrogen and hydroxyl intermediates on Ru by d-p orbital hybridization for hydrogen electrooxidation.

Strengthening the hydroxyl binding energy (OHBE) on Ru surfaces for efficient hydrogen oxidation reaction (HOR) in alkaline electrolytes at the expense of narrowing the effective potential window (EPW) increases the risk of passivation under transient conditions for the alkaline exchange membrane fuel cell technique. Herein, an effective Ru/NiSe2 catalyst was reported which exhibits a gradually enhanced intrinsic activity and slightly enlarged EPW with the increased degree of coupling between Ru and NiSe2. This promotion could be attributed to the optimized electron distribution and d-band structures of Ru surfaces weakening the hydrogen binding energy and especially the OHBE through the strong d-p orbital hybridization between Ru and NiSe2. Unlike the conventional way of strengthened OHBE enhancing the oxidative desorption of hydrogen intermediates (Had) via the bi-functional mechanism, the weakened OHBE on this Ru/NiSe2 model catalyst alleviates the competitive adsorption between Had and the hydroxyl intermediates (OHad), thereby accelerating the HOR kinetics at low overpotentials and hindering the full poisoning of the catalytic surfaces by strongly adsorbed OHad spectators at high overpotentials. The work reveals a missed but important approach for Ru-based catalyst development for the fuel cell technique.

Fluorescence correlation spectroscopy of repulsive systems: theory, simulation, and experiment.

The theoretical basis of fluorescence correlation spectroscopy (FCS) for repulsive systems, such as charged colloids or macromolecules, has been further expanded and developed. It is established that the collective correlation function can no longer be fitted using the theoretical model of non-interacting systems. Also, it is discovered that the collective correlation function can be divided into two parts: a self-part and a distinct-part, named as the self-correlation and cross-correlation function, respectively. The former indicates the self-diffusion of objects, while the latter describes mutual interactions. Dual-color fluorescence cross-correlation spectroscopy provides the direct measurements of the two parts. The particle concentration and mean squared displacement of single particles can be deduced from the self-correlation function, while the correlation volume between particles can be approximated from the cross-correlation function. In the case of charged colloids, the Debye length of the solution and particle surface charge number can be fitted from the cross-correlation function. These theoretical results are successfully proven using Brownian dynamics simulations and preliminary FCS experiments for model charged colloidal systems.

Improving collegiate student-athletes' well-being: exploring the roles of openness to experience, knowledge sharing and perceived coaching effectiveness.

Introduction: Collegiate student-athletes often encounter various stressors stemming from academic study and athletic training, which can potentially have negative effects on their well-being. This study investigates how collegiate student-athletes' openness to experience and their engagement in knowledge sharing influence their well-being, as well as the moderating role of perceived coaching effectiveness. Methods: To examine these relationships, we propose and test a conceptual framework using an online survey conducted among collegiate student-athletes from a southeastern province of China. The participants consisted of 484 collegiate student-athletes who voluntarily participated in the study. We used regression analysis and mediation analysis to test the proposed relationships among the variables. Results: Openness to experience has a positive impact on knowledge sharing (ß = 0.552, p < 0.05); knowledge sharing with peers positively affects collegiate student-athlete well-being (ß = 0.415, p < 0.05) and mediates the relationship between openness to experience and collegiate student-athlete well-being (ß = 0.086, p < 0.05). Perceived coaching effectiveness positively moderates the relationship between openness to experience and knowledge sharing (ß = 0.170, p < 0.05). Discussion: Our study contributes to the collegiate student-athlete literature by shedding light on the factors that influence their well-being, with insights that bear important managerial implications for universities and coaches.

An efficient bi-functional Ir-based catalyst for the acidic overall water splitting reaction.

Bi-functional catalytic ability of an Ir-based catalyst for the acidic overall water splitting reaction was realized using tellurium nanorods as a support resulting from the special electronic coupling and synergism of the Ir and Te elements.

Recent advances in iridium-based catalysts with different dimensions for the acidic oxygen evolution reaction.

Proton exchange membrane (PEM) water electrolysis is considered a promising technology for green hydrogen production, and iridium (Ir)-based catalysts are the best materials for anodic oxygen evolution reactions (OER) owing to their high stability and anti-corrosion ability in a strong acid electrolyte. The properties of Ir-based nanocatalysts can be tuned by rational dimension engineering, which has received intensive attention recently for catalysis ability boosting. To achieve a comprehensive understanding of the structural and catalysis performance, herein, an overview of the recent progress was provided for Ir-based catalysts with different dimensions for the acidic OER. The promotional effect was first presented in terms of the nano-size effect, synergistic effect, and electronic effect based on the dimensional effect, then the latest progress of Ir-based catalysts classified into zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D) catalysts was introduced in detail; and the practical application of some typical examples in the real PEM water electrolyzers (PEMWE) was also presented. Finally, the problems and challenges faced by current dimensionally engineered Ir-based catalysts in acidic electrolytes were discussed. It is concluded that the increased surface area and catalytic active sites can be realized by dimensional engineering strategies, while the controllable synthesis of different dimensional structured catalysts is still a great challenge, and the correlation between structure and performance, especially for the structural evolution during the electrochemical operation process, should be probed in depth. Hopefully, this effort could help understand the progress of dimensional engineering of Ir-based catalysts in OER catalysis and contribute to the design and preparation of novel efficient Ir-based catalysts.

MOF-derived transition metal-based catalysts for the electrochemical reduction of CO2 to CO: a mini review.

The excessive emission of CO2 derived from the consumption of fossil fuels has caused severe energy and environmental crises. The electrochemical reduction of CO2 into value-added products such as CO not only reduces the CO2 concentration in the atmosphere but also promotes sustainable development in chemical engineering. Thus, tremendous work has been devoted to developing highly efficient catalysts for the selective CO2 reduction reaction (CO2RR). Recently, MOF-derived transition metal-based catalysts have shown great potential for the CO2RR due to their various compositions, adjustable structures, competitive ability, and acceptable cost. Herein, based on our work, a mini-review is proposed for an MOF-derived transition metal-based catalyst for the electrochemical reduction of CO2 to CO. The catalytic mechanism of the CO2RR was first introduced, and then we summarized and analyzed the MOF-derived transition metal-based catalysts in terms of MOF-derived single atomic metal-based catalysts and MOF-derived metal nanoparticle-based catalysts. Finally, we present the challenges and perspectives for the subject topic. Hopefully, this review could be helpful and instructive for the design and application of MOF-derived transition metal-based catalysts for the selective CO2RR to CO.