Designing hybrid transition metal phosphosulfide electrocatalysts is critical for the hydrogen evolution reaction (HER). We propose a novel approach by designing a hierarchical structure of cobalt phosphide (CoP) and nickel phosphide (NiP) nanoparticles topotactically developed on nickel sulfide (NiS) nanorods (CoNiP/NiS) a sulfuration-phosphorization strategy using conductive 3D nickel foam. Hierarchical heterostructured nanorods were achieved without the need for template removal steps or the assistance of surfactants.
View Article and Find Full Text PDFThe development of an excellent multifunctional electrocatalyst that is based on non-precious metal is critical for improving the electrochemical processes of the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the urea oxidation reaction (UOR) in alkaline media. This study demonstrates that incorporating Mo into CoO facilitated the formation of rich oxygen vacancies (Vo), which promotes effective nitrate adsorption and activation in urea electrolysis. Subsequently, in situ/operando X-ray absorption spectroscopy is used to explore the active sites in Mo-CoO-3 under OER, indicating the oxygen vacancies are first filled with OH in Mo-CoO; facilitated the pre-oxidation of low-valence Co, and promoted the reconstruction/deprotonation of intermediate Co-OOH.
View Article and Find Full Text PDFRechargeable zinc-air batteries (ZABs) are viewed as a promising solution for electric vehicles due to their potential to provide a clean, cost-effective, and sustainable energy storage system for the next generation. Nevertheless, sluggish kinetics of the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR) at the air electrode, and low power density are significant challenges that hinder the practical application of ZABs. The key to resolving the development of ZABs is developing an affordable, efficient, and stable catalyst with bifunctional catalytic.
View Article and Find Full Text PDFEnviron Sci Technol
September 2024
Acid mine drainage (AMD) raises a global environmental concern impacting the iron cycle. Although the formation of Fe(III) minerals in AMD-impacted waters has previously been reported to be regulated by biological processes, the role of abiotic processes remains largely unknown. This study first reported that a photochemical reaction coupled with O significantly accelerated the formation of Fe(III) flocculates (i.
View Article and Find Full Text PDFACS Appl Mater Interfaces
September 2024
Electrochemical approaches for generating hydrogen from water splitting can be more promising if the challenges in the anodic oxygen evolution reaction (OER) can be harnessed. The interface heterostructure materials offer strong electronic coupling and appropriate charge transport at the interface regions, promoting accessible active sites to prompt kinetics and optimize the adsorption-desorption of active species. Herein, we have designed an efficient multi-interface-engineered NiFe LDH/NiS/TW heterostructure on in situ generated titanate web layers from the titanium foam.
View Article and Find Full Text PDFIron minerals in nature are pivotal hosts for heavy metals, significantly influencing their geochemical cycling and eventual fate. It is generally accepted that, vivianite, a prevalent iron phosphate mineral in aquatic and terrestrial environments, exhibits a limited capacity for adsorbing cationic heavy metals. However, our study unveils a remarkable phenomenon that the synergistic interaction between sulfide (S) and vivianite triggers an unexpected sulfidation-reoxidation process, enhancing the immobilization of heavy metals such as cadmium (Cd), copper (Cu), and zinc (Zn).
View Article and Find Full Text PDFUnderstanding the nucleation and growth mechanism of 3d transition bimetallic nanocrystals (NCs) is crucial to developing NCs with tailored nanostructures and properties. However, it remains a significant challenge due to the complexity of 3d bimetallic NCs formation and their sensitivity to oxygen. Here, by combining electron microscopy and synchrotron X-ray techniques, we elucidate the nucleation and growth pathways of Fe-Ni NCs.
View Article and Find Full Text PDFThe different electrolyte conditions, e.g., pH value, for driving efficient HER and OER are one of the major issues hindering the aim for electrocatalytic water splitting in a high efficiency.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2024
While efficient for electrochemical hydrogen evolution reaction (HER), Pt is limited by its cost and rarity. Traditional Pt catalysts and Pt single-atom (aPt) catalysts (Pt-SACs) face challenges in maintaining kinetically favorable HER pathways (Volmer-Tafel) at ultralow Pt loadings. Herein, carbon-promoted aPts were deposited on RuO without the addition of reductants.
View Article and Find Full Text PDFAn AA'BB'O-type quadruple perovskite oxide of CaCuCrReO was synthesized at 18 GPa and 1373 K. Both an A- and B-site ordered quadruple perovskite crystal structure was observed, with the space group -3. The valence states are verified to be CaCuCrReO by bond valence sum calculations and synchrotron X-ray absorption spectroscopy.
View Article and Find Full Text PDFDeveloping atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO. Ethylene selectivity and utilization of converted CO can reach 100 % and 99.
View Article and Find Full Text PDFThe coupled NO-vibrational peaks [IR ν 1775 s, 1716 vs, 1668 vs cm (THF)] between two adjacent [Fe(NO)] groups implicate the electron delocalization nature of the singly -phenoxide-bridged dinuclear dinitrosyliron complex (DNIC) [Fe(NO)(μ-ON)Fe(NO)] (). Electronic interplay between [Fe(NO)] units and [ON] ligand in DNIC rationalizes that "hard" -phenoxide moiety polarizes iron center(s) of [Fe(NO)] unit(s) to enforce a "constrained" π-conjugation system acting as an electron reservoir to bestow the spin-frustrated {Fe(NO)}-{Fe(NO)}-[ON] electron configuration ( = 1/2). This system plays a crucial role in facilitating the ligand-based redox interconversion, working in harmony to control the storage and redox-triggered transport of the [Fe(NO)] unit, while preserving the {Fe(NO)} core in DNICs {Fe(NO)}-[ON] [K-18-crown-6-ether)][(ON)Fe(NO)] () and {Fe(NO)}-[ON] [(ON)Fe(NO)][PF] ().
View Article and Find Full Text PDFSingle-atom catalysts, known for their high activity, have garnered significant interest. Currently, single-atom catalysts were prepared mainly on 2D substrates with random distribution. Here, we report a strategy for preparing arrayed single Pt (Pt) atoms, which are templated through coordination with phosphotungstic acids (PTA) intercalated inside hexagonally packed silicate nanochannels for a high single Pt-atom loading of ca.
View Article and Find Full Text PDFTo investigate synergistic effect between geometric and electronic structures on directing CORR selectivity, water phase synthetic protocol and surface architecture engineering strategy are developed to construct monodispersed Bi-doped Cu-based nanocatalysts. The strongly correlated catalytic directionality and Bi dopant can be rationalized by the regulation of [*COOH]/[*CO] adsorption capacities through the appropriate doping of Bi electronic modulator, resulting in volcano relationship between FE/TOF and surface EVBM values. Spectroscopic study reveals that the dual-site binding mode ([Cu─μ─C(═O)O─Bi]) enabled by CuBi motif in single-phase CuBi nanocatalyst drives CO2-to-CO conversion.
View Article and Find Full Text PDFElectron modulation presents a captivating approach to fabricate efficient electrocatalysts for the oxygen evolution reaction (OER), yet it remains a challenging undertaking. In this study, an effective strategy is proposed to regulate the electronic structure of metal-organic frameworks (MOFs) by the construction of MOF-on-MOF heterogeneous architectures. As a representative heterogeneous architectures, MOF-74 on MOF-274 hybrids are in situ prepared on 3D metal substrates (NiFe alloy foam (NFF)) via a two-step self-assembly method, resulting in MOF-(74 + 274)@NFF.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2024
As a crucial stage of electrochemical water splitting, hydrogen evolution reaction (HER) favour catalyst to attain rapid kinetics for its broader application, alternating Pt in the acidic environment. Transition metal phosphides (TMPs) are one kind of earth-abundant, nonprecious-based catalyst which has been classified as a viable alternative and active for HER. While the performance remains inferior to Pt which primarily targets durability under high current density, pinpointing the reconfiguration strategy would be critical to their catalytic competency.
View Article and Find Full Text PDFResearchers are investigating innovative composite materials for renewable energy and energy storage systems. The major goals of this studies are i) to develop a low-cost and stable trimetallic oxide catalyst and ii) to change the electrical environment of the active sites through site-selective Mo substitution. The effect of Mo on NiCoMoO is elucidated using both in situ X-ray absorption spectroscopy and X-ray diffraction analysis.
View Article and Find Full Text PDFWe report two novel three-dimensional copper-benzoquinoid metal-organic frameworks (MOFs), [Cu L ] and [Cu L ⋅ Cu(iq) ] (LH =1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal-organic extended solids.
View Article and Find Full Text PDFMethane pyrolysis (MP) is a potential technology for CO-free hydrogen production that generates only solid carbon by-products. However, developing a highly efficient catalyst for stable methane pyrolysis at a moderate temperature has been challenging. We present a new and highly efficient catalyst created by modifying a Ni-Bi liquid alloy with the addition of Mo to produce a ternary NiMo-Bi liquid alloy catalyst (LAC).
View Article and Find Full Text PDFLigands and additives are often utilized to stabilize low-valent catalytic metal species experimentally, while their role in suppressing metal deposition has been less studied. Herein, an on-cycle mechanism is reported for CoClbpy catalyzed Negishi-type cross-coupling. A full catalytic cycle of this kind of reaction was elucidated by multiple spectroscopic studies.
View Article and Find Full Text PDF-Nitrosothiols (SNOs) serve as endogenous carriers and donors of NO within living cells, releasing nitrosonium ions (NO), NO, or other nitroso derivatives. In this study, we present a bioinspired {Co(NO)} complex 1 that achieved -nitrosation towards Cys residues. The incorporation of a ferrocenyl group in 1 allowed for fine-tuning of the nitrosation reaction, taking advantage of the redox ability of Cys residues.
View Article and Find Full Text PDFIn this work, we studied the optical properties of Dy-doped GdO nanoparticles (NPs) before and after their APTES functionalisation. We obtained luminescent Dy@GdO NPs (0.5, 1, and 5% mol) using a modified polyol method.
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