Anchoring Ni(OH)2-CeOx Heterostructure on FeOOH-Modified Nickel-Mesh for Efficient Alkaline Water-Splitting Performance with Improved Stability under Quasi-Industrial Conditions.

Developing low-cost and industrially viable electrode materials for efficient water-splitting performance and constructing intrinsically active materials with abundant active sites is still challenging. In this study, a self-supported porous network Ni(OH)2-CeOx heterostructure layer on a FeOOH-modified Ni-mesh (NiCe/Fe@NM) electrode is successfully prepared by a facile, scalable two-electrode electrodeposition strategy for overall alkaline water splitting. The optimized NiCe0.05/Fe@NM catalyst reaches a current density of 100 mA cm-2 at an overpotential of 163 and 262 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1.0 m KOH with excellent stability. Additionally, NiCe0.05/Fe@NM demonstrates exceptional HER performance in alkaline seawater, requiring only 148 mV overpotential at 100 mA cm-2. Under real water splitting conditions, NiCe0.05/Fe@NM requires only 1.701 V to achieve 100 mA cm-2 with robust stability over 1000 h in an alkaline medium. The remarkable water-splitting performance and stability of the NiCe0.05/Fe@NM catalyst result from a synergistic combination of factors, including well-optimized surface and electronic structures facilitated by an optimal Ce ratio, rapid reaction kinetics, a superhydrophilic/superaerophobic interface, and enhanced intrinsic catalytic activity. This study presents a simple two-electrode electrodeposition method for the scalable production of self-supported electrocatalysts, paving the way for their practical application in industrial water-splitting processes.

Synergistically Coupled Ni/CeOx@C Electrocatalysts for the Hydrogen Evolution Reaction: Remarkable Performance to Pt/C at High Current Density.

Incredibly active electrocatalysts comprising earth-abundant materials that operate as effectively as noble metal catalysts are essential for the sustainable generation of hydrogen through water splitting. However, the vast majority of active catalysts are produced via complicated synthetic processes, making scale-up considerably tricky. In this work, a facile strategy is developed to synthesize superhydrophilic Ni/CeOx nanoparticles (NPs) integrated into porous carbon (Ni/CeOx@C) by a simple two-step synthesis strategy as efficient hydrogen evolution reaction (HER) electrocatalysts in 1.0 M KOH. Benefiting from the electron transport induced by the heterogeneous interface between Ni and CeOx NPs and the superhydrophilic structure of the catalyst, the resultant Ni2Ce1@C/500 catalysts exhibit a low overpotential of 26 and 184 mV at a current density of 10 and 300 mA cm-2, respectively, for HER with a small Tafel slope of 62.03 mV dec-1 and robust durability over 300 h, and its overpotential at a high current density is much better than the benchmark commercial Pt/C. Results revealed that the electronic rearrangement between Ni and CeOx integrated into porous carbon could effectively regulate the local conductivity and charge density. In addition, the oxygen vacancies and Ni/CeOx heterointerface promote water adsorption and hydrogen intermediate dissociation into H2 molecules, which ultimately accelerate the HER reaction kinetics. Notably, the electrochemical results demonstrate that structural optimization by regulating synthesis temperature and metal concentration could improve the surface features contributing to high electrical conductivity and increase the number of electrochemically active sites on the Ni/CeOx@C heterointerface, high crystal purity, and better electrical conductivity, resulting in its exceptional electrocatalytic performance toward the HER. These results indicated that the Ni/CeOx@C electrocatalyst has the potential for practical water-splitting applications because of its controlled production strategy and outstanding Pt-like HER performance.

Emerging transition metal and carbon nanomaterial hybrids as electrocatalysts for water splitting: a brief review.

Electrocatalytic water splitting has appeared to be a sustainable green technology for hydrogen and oxygen production, and noble metal-based electrocatalysts, like Pt for hydrogen evolution reaction (HER) and RuO2/IrO2 for oxygen evolution reaction (OER) have been proved to be state-of-the-art in water electrolyzers. However, high cost and scarcity of noble metals hinder large-scale applications of these electrocatalysts in practical commercial water electrolyzers. As an alternative, transition metal based electrocatalysts have attracted great attention because of the exciting catalytic performance, cost-effectiveness and abundant availability. However, their long-term stability in water splitting devices is unsatisfactory because of agglomeration and dissolution in the harsh operating environment. A possible solution to this issue is encapsulating transition metal (TM) based materials in stable and highly conductive carbon nanomaterials (CNMs) to make a hybrid of TM/CNMs, and the performance of TM/CNMs could be further enhanced by heteroatom (N-, B-, and dual N,B-) doping to carbon network in CNMs to break the carbon electroneutrality due to the different electronegativity, modulate the electronic structure to facilitate the adsorption of reaction intermediates, and promotion of efficient electron transfer to enhance the number of catalytically active sites for water splitting operation. In this review article, the recent progress of TM-based materials hybridizing with CNMs, N-CNMs, B-CNMs, and N,B-CNMs as electrocatalysts towards HER, OER as well as overall water splitting have been summarized, and the challenges and future prospects are also discussed.

Insights of keratin geometry from agro-industrial wastes: A comparative computational and experimental assessment.

Understanding the structural properties of keratin is of great importance to managing their potential application in keratin-inspired biomaterials and its management of wastes. In this work, the molecular structure of chicken feather keratin 1 was characterized by AlphaFold2 and quantum chemistry calculation. The predicted IR spectrum of the N-terminal region of feather keratin 1, consisting of 28 amino acid residues, was used to assign the Raman frequencies of the extracted keratin. The MW of experimental samples were 6 & 1 kDa while the predicted MW (∼10 kDa) of ß-keratin. Experimental analysis shows the magnetic field treatment could affect the functional and surface structural properties of keratin. The particle size distribution curve illustrates the dispersion of particle size concentration, while TEM analysis demonstrates the reduction of particle diameter to 23.71 ± 1.1 nm following treatment. High-resolution XPS analysis confirmed the displacement of molecular elements from their orbital.

Recent advances in understanding and design of efficient hydrogen evolution electrocatalysts for water splitting: A comprehensive review.

An unsustainable reliance on fossil fuels is the primary cause of the vast majority of greenhouse gas emissions, which in turn lead to climate change. Green hydrogen (H2), which may be generated by electrolyzing water with renewable power sources, is a possible substitute for fossil fuels. On the other hand, the increasing intricacy of hydrogen evolution electrocatalysts that are presently being explored makes it more challenging to integrate catalytic theories, catalytic fabrication procedures, and characterization techniques. This review will initially present the thermodynamics, kinetics, and associated electrical and structural characteristics for HER electrocatalysts before highlighting design approaches for the electrocatalysts. Secondly, an in-depth discussion regarding the rational design, synthesis, mechanistic insight, and performance improvement of electrocatalysts is centered on both the intrinsic and extrinsic influences. Thirdly, the most recent technological advances in electrocatalytic water-splitting approaches are described. Finally, the difficulties and possibilities associated with generating extremely effective HER electrocatalysts for water-splitting applications are discussed.

Progress toward Polymerization Reaction Monitoring with Different Dienes: How Small Amounts of Dienes Affect ansa-Zirconocenes/Borate/Triisobutylaluminium Catalyst Systems.

The objectives of this work were to address the fundamental characteristics of ansa-zirconocene catalyzed E/diene copolymerization and E/diene/1-hexene and E/diene/propylene terpolymerizations, and the quantitative relationship between diene structure and polymer chain propagation rate constant in term of quantifiable catalytic active sites. One of the most important but unknown factors in olefins ansa-zirconocene complexes is the distribution of the catalyst between sites actively participating in polymer chain formation and dormant sites. A set of ethylene/dienes copolymerizations, and ethylene/dienes/1-hexene and ethylene/dienes/1-hexene terpolymerizations catalyzed with ansa-zirconocenes/borate/triisobutylaluminium (rac-Et(Ind)2ZrCl2/[Ph3C][B(C6F5)4]/triisobutylaluminium (TIBA) were performed in toluene at 50 °C To determine the active center [C*]/[Zr] ratio variation in the copolymerization of E with different dienes and their terpolymerization with 1-hexene and propylene, each polymer propagation chain ends were quenched with 2-thiophenecarbonyl, which selectively quenches the metal-polymer bonds through acyl chloride. The ethylene, propylene, 1-hexene, and diene composition-based propagation rate constants (kpE, kpP, kp1-H, and kpdiene), thermal (melting and crystalline) properties, composition (mol% of ethylene, propylene, 1-hexene, and diene), molecular weight, and polydispersity were also studied in this work. Systematic comparisons of the proportion of catalytically [Zr]/[C*] active sites and polymerization rate constant (kp) for ansa-zirconocenes catalyzed E/diene, E/diene/1-hexene, and E/diene/propylene polymerization have not been reported before. We evaluated the addition of 1-hexene and propylene as termonomers in the copolymerization with E/diene. To make a comparison for each diene under identical conditions, we started the polymerization by introducing an 80/20 mole ratio of E/P and 0.12 mol/L of 1-hexene in the system. The catalyst behavior against different dienes, 1-hexene, and propylene is very interesting, including changes in thermal properties, cyclization of 1-hexene, and decreased incorporation of isoprene and butadiene, changes in the diffusion barriers in the system, and its effect on kp.

Ni3S2 nanostrips@FeNi-NiFe2O4 nanoparticles embedded in N-doped carbon microsphere: An improved electrocatalyst for oxygen evolution reaction.

The designing and preparing of low-cost and easily available electrocatalyst for oxygen evolution reaction (OER) are crucial for many advanced energy technologies. Herein, the Ni3S2 nanostrips@FeNi-NiFe2O4 nanoparticles embedded in N-doped carbon (Ni3S2@FeNi-NiFe2O4/C) microspheres were synthesized as improved electrocatalyst for OER, using a facile heat-treatment method. The optimized Ni3S2@FeNi-NiFe2O4/C-3 sample exhibits enhanced electrocatalytic activity toward OER performance with an overpotential of 280 mV at 10 mA cm-2 and a small Tafel slope of 33.9 mV dec-1. Furthermore, Ni3S2@FeNi-NiFe2O4/C-3 composite shows good stability in alkaline media. The outstanding electrocatalytic OER performance of composites was attributed due to the synergetic effect between Ni3S2 nanostrips and FeNi-NiFe2O4 nanoparticles and it is believed that the heterointerfaces between them act as active centers for OER. Additionally, N-doped carbon prevents the aggregation of Ni3S2@FeNi-NiFe2O4 species and enhances the conductivity of composites during the OER process.

Comparative Analysis of Ethylene/Diene Copolymerization and Ethylene/Propylene/Diene Terpolymerization Using Ansa-Zirconocene Catalyst with Alkylaluminum/Borate Activator: The Effect of Conjugated and Nonconjugated Dienes on Catalytic Behavior and Polymer Microstructure.

The copolymerization of ethylene‒diene conjugates (butadiene (BD), isoprene (IP) and nonconjugates (5-ethylidene-2-norbornene (ENB), vinyl norbornene VNB, 4-vinylcyclohexene (VCH) and 1, 4-hexadiene (HD)), and terpolymerization of ethylene-propylene-diene conjugates (BD, IP) and nonconjugates (ENB, VNB, VCH and HD) using two traditional catalysts of C2-symmetric metallocene-silylene-bridged rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2 (complex A) and ethylene-bridged rac-Et(Ind)2ZrCl2 (complex B)-with a [Ph3C][B(C6F5)4] borate/TIBA co-catalyst, were intensively studied. Compared to that in the copolymerization of ethylene diene, the catalytic activity was more significant in E/P/diene terpolymerization. We obtained a maximum yield of both metallocene catalysts with conjugated diene between 3.00 × 106 g/molMt·h and 5.00 × 106 g/molMt·h. ENB had the highest deactivation impact on complex A, and HD had the most substantial deactivation effect on complex B. A 1H NMR study suggests that dienes were incorporated into the co/ter polymers' backbone through regioselectivity. ENB and VNB, inserted by the edo double bond, left the ethylidene double bond intact, so VCH had an exo double bond. Complex A's methyl and phenyl groups rendered it structurally stable and exhibited a dihedral angle greater than that of complex B, resulting in 1, 2 isoprene insertion higher than 1, 4 isoprene that is usually incapable of polymerization coordination. High efficiency in terms of co- and ter- monomer incorporation with higher molecular weight was found for complex 1. The rate of incorporation of ethylene and propylene in the terpolymer backbone structure may also be altered by the conjugated and nonconjugated dienes. 13C-NMR, 1H-NMR, and GPC techniques were used to characterize the polymers obtained.