Earth-abundant Metal Research Articles

Sustainable photocatalytic hydrogen peroxide production over octonary high-entropy oxide

The direct utilization of solar energy for the artificial photosynthesis of hydrogen peroxide (H2O2) provides a reliable approach for producing this high-value green oxidant. Here we report on the utility of high-entropy oxide (HEO) semiconductor as an all-in-one photocatalyst for visible light-driven H2O2 production directly from H2O and atmospheric O2 without the need of any additional cocatalysts or sacrificial agents. This high-entropy photocatalyst contains eight earth-abundant metal elements (Ti/V/Cr/Nb/Mo/W/Al/Cu) homogeneously arranged within a single rutile phase, and the intrinsic chemical complexity along with the presence of a high density of oxygen vacancies endow high-entropy photocatalyst with distinct broadband light harvesting capability. An efficient H2O2 production rate with an apparent quantum yield of 38.8% at 550 nm can be achieved. The high-entropy photocatalyst can be readily assembled into floating artificial leaves for sustained on-site production of H2O2 from open water resources under natural sunlight irradiation.

Influence of Annealing Temperature on the OER Activity of NiO(111) Nanosheets Prepared via Microwave and Solvothermal Synthesis Approaches.

Earth-abundant transition metal oxides are promising alternatives to precious metal oxides as electrocatalysts for the oxygen evolution reaction (OER) and are intensively investigated for alkaline water electrolysis. OER electrocatalysis, like most other catalytic reactions, is surface-initiated, and the catalyst performance is fundamentally determined by the surface properties. Most transition metal oxide catalysts show OER activities that depend on the predominantly exposed crystal facets/surface structure. Therefore, the design of synthetic strategies to obtain the most active crystal facets is of significant research interest. In this work, rock salt NiO OER catalysts with (111) predominantly exposed facets were synthesized by a solvothermal (ST) method either heated under supercritical or microwave-assisted (MW) conditions. Particular emphasis was placed on the influence of the post annealing temperature on the structural configuration and OER activity to compare their catalytic performances. The as-prepared electrocatalysts are pure α-Ni hydroxides which were converted to rock salt NiO (111) nanosheets with hexagonal pores after heat treatment at different temperatures. The OER activity of the electrodes has been evaluated in 0.1 M KOH using geometric and intrinsic current densities via normalization by the disk area and BET area, respectively. The lowest overpotential at a geometric current density of 10 mA/cm2 is found for samples pretreated by heating between 400 and 500 °C with a catalyst loading of 115 μg/cm2. Despite the very similar nature of the catalysts obtained from the two methods, the ST electrodes show a higher geometric and intrinsic current density for 500 °C pretreatment. The MW electrodes, however, achieve an optimal geometric current density for 400 °C pretreatment, while their intrinsic current density requires pretreatment over 600 °C. Interestingly, pretreated electrodes show consistently higher OER activity as compared to the poorly crystalline/less ordered hydroxide as-prepared electrocatalysts. Thus, our study highlights the importance of the synthesis method and pretreatment at an optimal temperature.

Developing zirconium xerogel coagulants for deep removal of phosphorous

Deep removal of phosphorous (P) from water is a necessary measure to solve the eutrophication problem. Coagulation is both a basic treatment method for P removal and an important pretreatment process for membrane filtration. However, few coagulants can meet the both requirements. Based on the analysis on the hydrolysis behaviors of some earth-abundant metals and the solubility products of their phosphates, a series of zirconium xerogel coagulants (ZXC) was fabricated with a novel approach (the sol-gel method) and was evaluated for the removal of both organic and inorganic P in coagulation and coagulation-ultrafiltration. In terms of P removal and anti-fouling of membrane, the resultant ZXC outperformed polyzirconium chloride (PZC), polyaluminum chloride (PAC), polyferric sulfate (PFS), as well as titanium xerogel coagulant (TXC) in a wide range of pH and dose. The rapid hydrolysis of Zr4+ and the formation of Zr3(PO4)4 with a rather low solubility product are attributable to the great performance of ZXC in coagulation. This study highlights the potential of ZXC as an effective solution for enhancing the treatment of water and wastewater, particularly in achieving deep P removal and improving membrane fouling resistance, thereby contributing to more sustainable and efficient strategies for addressing eutrophication and pollutant removal.

Colloidal Bimetallic RuNi Particles and their Behaviour in Catalytic Quinoline Hydrogenation.

Colloidal metal nanoparticles exhibit interesting catalytic properties for the hydrogenation of (hetero)arenes. Catalysts based on precious metals, such as Ru and Rh, promote this reaction efficiently under mild reaction conditions. In contrast, heterogeneous catalysts based on earth-abundant metals can selectively hydrogenate (hetero)arenes but require harsher reaction conditions. Bimetallic catalysts that combine precious and earth-abundant metals are interesting materials to mitigate the drawbacks of each component. To this end, RuNi nanoparticles bearing a phosphine ligand were prepared through the decomposition of [Ru(η4-C8H12)(η6-C8H10)] and [Ni(η4-C8H12)2] by H2 at 85 °C. Wide angle X-ray scattering confirmed a bimetallic segregated structure, with Ni predominantly on the surface. Spectroscopic analyses revealed that the phosphine ligand coordinated to the surface of both metals, suggesting, as well, a partial Ni shell covering the Ru core. The RuNi-based nanomaterials were used as catalysts in the hydrogenation of quinoline to assess the impact of the metallic composition and of the stabilizing agent on their catalytic performance.

Selective Monoborylation of Methane by a Mono Bipyridyl-Nickel(II)Hydride Catalyst.

We report the development of an earth-abundant metal catalyst for methane C‒H borylation. The post-synthetic metalation of bipyridine-functionalized zirconium metal-organic framework (MOF) with NiBr2, followed by treatment of NaEt3BH affords MOF-supported monomeric bipyridyl-nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 ºC using pinacolborane (HBpin) to afford CH3Bpin in 61% yield with a turnover number (TON) up to 1388. The confinement of the active NiH2-species within the uniformly porous MOF allows selective monoborylation of methane via shape-selective catalysis by preventing the formation of sterically encumbered overborylated products. Unlike MOF-Ni catalyst, its homogeneous control is almost inactive in methane borylation due to its intermolecular decomposition. Our mechanistic investigation, including spectroscopic, kinetic, and control experiments, as well as DFT calculations, revealed that stabilizing mononuclear bipyridyl-nickel dihydride and diboryl species by MOF is crucial for achieving efficient methane borylation via turnover-limiting σ-bond metathesis. This work shows promise in designing MOF-based abundant metal catalysts for the chemoselective functionalization of methane and other inert molecules into valuable chemicals.

DFT analysis of the concerted metalation-deprotonation in earth-abundant 3d-transition-metal mediated C–H activations

Methane activation and functionalization under catalytic conditions remains a challenge that must be addressed to make this abundant alkane, the primary component of natural gas, into a more useful resource. One possible method of methane activation is concerted metalation-deprotonation (CMD), which thus far has been largely limited to precious metals and more reactive substrates. In this DFT study, CMD activation of methane is assessed employing more earth-abundant 3d transition metal complexes to assess the effects of metal, ligands, etc. upon the kinetics and thermodynamics of methane C–H activation via CMD mechanisms. Key findings from this study reveal the strong influence spin states as well as ligand modification have on the activation energy barriers. Moreover, an unexpected observation pertaining to ligand modification was seen where the acetate ligand exhibited higher computed free energy barriers compared to the trifluoroacetate ligand. Although acetate is more basic than trifluoroacetate, the ligand directing effects ultimately had a greater influence on the thermodynamic control of the CMD mechanism being studied here.

Redox-mediated synthesis of Cu2O/CuO/Mn3O4/C quaternary nanocomposites as an efficient electrode material for oxygen reduction reaction and supercapacitor application

Earth-abundant transition metal oxides (TMOs) hold significant promise as electroactive materials in various electrochemical energy conversion and storage applications, offering economic and environmental advantages over their less abundant counterparts. In this work, a simple and cost-effective redox-mediated reaction strategy under hydrothermal conditions has been adopted to synthesize the quaternary nanocomposites Cu2O/CuO/Mn3O4/C with variable amounts of carbon. The synthesized nanocomposites have been characterized using various analysis techniques, including powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Brunauer–Emmett–Teller (BET). The synthesized COM5 nanocomposite (Cu2O/CuO/Mn3O4/C-50), when used as an electrocatalyst for the oxygen reduction reaction (ORR), demonstrates a good limiting current density (JL), half-wave potential (E1/2), and onset potential (Eonset) of −5.50 mA/cm2, 0.75 V, and 0.95 V, respectively, as per the polarization curve. The COM5 nanocomposite exhibits a four-electron transfer mechanism, calculated using the Koutecky-Levich (K-L) equation. In an O2-saturated 0.1M KOH solution, the COM5 nanocomposite has shown a superior relative current durability of 84.46% over 14,000 s compared to the commercially available 10 wt% Pt/C, indicating its potential application in the ORR. However, for supercapacitor applications, the COM3 nanocomposite (Cu2O/CuO/Mn3O4/C-20) as active electrode material in galvanic charge-discharge (GCD) study shows superior performance (201 F/g at 1 A/g) compared to the COM2 nanocomposite (117 F/g at 1 A/g) in neutral aqueous electrolyte, possibly due to the lower charge transfer resistance (Rct) of 24.04 Ω compared to COM2 (34.63 Ω). In two-electrode studies, the COM3 nanocomposite exhibits a good energy density of 24.19 Wh/kg at 1 A/g and a 4.7 kW/kg power density at 5 A/g. Additionally, the COM3 nanocomposite shows excellent long-term durability (74% capacitance retention) at the current density of 5 A/g for 8000 cycles. The electrochemical findings indicate that the COM3 nanocomposite stands out as a superior electrode material for supercapacitors, while the COM5 nanocomposite proves to be an effective electrocatalyst for the oxygen reduction reaction.

Mechanism Insight into Direct Amidation Catalyzed by Zr Salts: Evidence of Zr Oxo Clusters as Active Species.

The capricious reactivity and speciation of earth-abundant metals (EAM) hinder the mechanistic understanding essential to boost their efficiency and versatility in catalysis. Moreover, metal's solution chemistry and reactivity are conventionally controlled using organic ligands, while their fundamental chemistry in operando conditions is often overlooked. However, in this study, we showcase how a better understanding of in operando conditions may result in improved catalytic reactions. By assessing the composition and structure of active species for Zr-catalyzed direct amide bond formations under operating conditions, we discovered zirconium oxo clusters form quickly and are likely active species in the reactions. Formation of these clusters dismisses the use of additional organic ligands, inert atmosphere, anhydrous solvents, or even water scavenging to provide amides in good to excellent yields. More specifically, dodeca- and hexazirconium oxo clusters (Zr12 and Zr6, respectively) rapidly form from commercial, readily available Zr salts under reaction conditions known to afford amides directly from nonactivated carboxylic acid and amine substrates. Extended X-ray absorption fine structure (EXAFS) experiments confirm the presence of oxo clusters in solution throughout the reaction, while their key role in the mechanism is supported by an in-depth computational study employing density functional theory (DFT) and molecular dynamics (MD) methods. These results underline the value of (earth-abundant) metals' intrinsic solution chemistry to transformative mechanistic understanding and to enhance the sustainability of organic transformations.

CuFe Cooperativity at the Membrane-Electrode Interface Elicits a Tandem 2e-+2e- Mechanism for Exclusive O2-To-H2O Electroreduction.

High O2 reduction reaction (ORR) kinetics and exclusive 4e- pathway selectivity are keys to realizing a sustainable society. However, nonprecious electrocatalysts at present cannot enhance the ORR turnover frequency and H2O Faradaic efficiency (FE) concurrently. To address these two challenges, hybrid bilayer membrane (HBM) electrodes with earth-abundant metal centers are developed to control proton-coupled electron transfer (PCET) in ORR. Here, an oxidase-inspired CuFe active site is supported on a tris(2-pyridylmethyl)amine HBM and explored as a unique interface for efficient ORR. This bimetallic HBM displayed an ORR activity 1.4 times higher than the monometallic systems and exhibited the highest FE for H2O (∼94%) among Cu-, Fe-, Ni-, and Co-based HBMs. Contrary to previous studies where the ORR current decreases upon embedding the metal center in a hydrophobic lipid environment, here, the incorporation of a nitrile-terminated proton carrier at the HBM interface boosts the ORR current by 1.7 folds relative to the case where the catalytic site is directly exposed to protons in solution. This intriguing dual improvement is supported by density function theory calculations where an additional 2e-+2e- mechanism occurs in parallel to the direct 4e- pathway, highlighting the synergistic effect of the CuFe HBM for facilitating high-performance ORR. A Zn-air battery is constructed using this CuFe HBM for the first time, further demonstrating that the knowledge gained from this HBM technology holds practical values in real-life applications. These findings on interfacial PCET are envisioned to spark new design principles for future catalysts with optimal electrochemical properties for advanced energy conversion schemes.

Prompt template-free synthesis of porous PtPb sponge-like nanostructure for electro-oxidation of methanol and carbon monoxide

Porous Pt-based alloys entail earth-abundant and low-cost metal, not only contribute to the rational consumption of expensive and rare Pt metal but also the enhancement of its activity towards the methanol electro-oxidation reaction (MEOR). Herein, a porous sponge-like PtPb alloy was synthesized by using the ice-reduction method driven by the coalescence growth mechanism under the intensive reduction power of borohydride. The presented PtPb sponge nanostructure was prepared using a facile, one-step method without heating or surfactants. Meanwhile, PtPb had a sponge-like shape with accessible active sites, a high surface area, abundant pore volume (0.05 cm3/g), pore size (2–20 nm), Pb loading (13.0 at.%), and an upshifted d-band center of Pt. These inimitable structural and compositional merits endow the electro-oxidation of methanol with a higher mass (specific) activity of 0.907 mA/µgPt (5.7 mA/cm2) compared to those of Pt sponge-like nanostructure and Pt/C catalyst by 1.47 (1.35) and 1.72 (8.51) times, respectively, besides higher durability. Moreover, PtPb had higher activity and durability towards the electro-oxidation of carbon monoxide (CO) than Pt and Pt/C. The proposed study may provide new insights into the simple synthesis of a Pt-based alloy for the electrocatalytic oxidation of small organic molecules.

Cobalt-Catalyzed Divergence in C(sp3)-H Functionalization of 9H-Fluorene: A Streamlined Approach Utilizing Alcohols.

Sustainable chemical production demands the creation of innovative catalysts and catalytic technologies. While the development of coherent and robust catalytic systems using earth-abundant transition metals is essential, it remains a significant challenge. Herein, an expedient divergence strategy for tandem dehydrogenative C(sp3)-H alkylation and cyclization reactions of 9H-fluorene using a newly developed N,N-bidentate cobalt catalytic system is developed. This method capitalizes on the use of abundant and readily accessible alcohol. Demonstrating wide-ranging applicability, the catalytic protocol successfully integrated a diverse array of fluorenes and alcohols. This includes benzylic, heteroaromatic, and aliphatic primary and secondary alcohols, amassing a total of 75 distinct examples. When applied to sterically bulky alcohols, the reaction preferentially undergoes alkenylation, yielding a tetrasubstituted olefin as the main product. In the case of diols, the expected outcome is Dual-fluorescence at both terminal positions. This process leads to difluorination, followed by a cyclization step, culminating in the formation of a relatively unprecedented spiro compound. The scalability of this method has been validated through gram-scale synthesis. Control experiments have shed light on the reaction mechanism, indicating that it progresses through an unsaturated intermediate and adheres to the borrowing hydrogen pathway.

Revealing Enhanced Active Oxygen Formation by Incorporating Chromium into Nickel Hydroxide Nanosheets for Improved Oxygen Evolution Reaction.

Nickel-based oxyhydroxides have emerged as promising catalysts for the oxygen evolution reaction (OER) among Earth-abundant metals. While the incorporation of foreign elements is recognized to enhance catalytic activity, the origin of this enhancement is still debated. We synthesize and examine Ni hydroxide nanosheets, both with and without Cr doping, to elucidate the underlying enhancements. Operando UV-vis and Raman spectroscopy are employed to unravel the behavior of the catalysts. The Cr doping facilitates the oxidation of Ni, resulting in the generation of active oxygen species. The enriched active oxygen species improves OER performance through a lattice oxygen-mediated pathway in Fe-free KOH, and further contribute to the creation and increased activity of FeOxHy sites in the presence of Fe impurities. This work provides a mechanistic understanding of the performance enhancement in Ni-based catalysts through Cr doping and suggests a strategy for the design of more efficient catalysts in the future.

Nanostructured NiMoO4 as an Efficient Electrocatalyst for Oxygen Evolution Reaction

Electrocatalysts derived from earth-abundant transition metals offer a viable alternative to noble metals for water electrolysis, yet they often suffer from poor catalytic behaviour and limited lifespan. In this study, nanostructured nickel molybdate on nickel foam (NiMoO4/NF) were synthesized via a straightforward hydrothermal process at three different durations (6, 12, and 24 h) to assess their oxygen evolution reaction (OER) performance. The electrodes, specifically NiMoO4-6h, NiMoO4-12h, and NiMoO4-24h, demonstrated significant OER activity in 1.0 M KOH solution, achieving overpotentials of 315 mV, 290 mV and 320 mV for respectively. Notably, the NiMoO4-12h electrode showed an exceptional stability, with only a 1.28% activity decrease after 200 hours at a current density of 10 mA cm-2. This study presents a novel approach to enhancing the electrocatalytic efficiency of these catalysts through optimizing their electrical conductivity, active surface sites, and surface reaction dynamics.

Nanostructured NiMoO4 as an Efficient Electrocatalyst for Oxygen Evolution Reaction

Electrocatalysts derived from earth-abundant transition metals offer a viable alternative to noble metals for water electrolysis, yet they often suffer from poor catalytic behaviour and limited lifespan. In this study, nanostructured nickel molybdate on nickel foam (NiMoO4/NF) were synthesized via a straightforward hydrothermal process at three different durations (6, 12, and 24 h) to assess their oxygen evolution reaction (OER) performance. The electrodes, specifically NiMoO4-6h, NiMoO4-12h, and NiMoO4-24h, demonstrated significant OER activity in 1.0 M KOH solution, achieving overpotentials of 315 mV, 290 mV and 320 mV for respectively. Notably, the NiMoO4-12h electrode showed an exceptional stability, with only a 1.28% activity decrease after 200 hours at a current density of 10 mA cm-2. This study presents a novel approach to enhancing the electrocatalytic efficiency of these catalysts through optimizing their electrical conductivity, active surface sites, and surface reaction dynamics.

Photo- and Electrocatalytic Hydrogen Evolution by Heteroleptic Dirhodium(II,II) Complexes: Role of the Bridging and Diimine Ligands.

A series of heteroleptic Rh2(II,II) complexes, cis-[Rh2(μ-DPhF)2(μ-bncn)2]2+ (1; bncn = benzo[c]cinnoline), cis-[Rh2(μ-DPhF)(μ-OAc)(μ-bncn)2]2+ (2), and cis-[Rh2(μ-OAc)2(μ-bncn)2]2+ (3), is presented, and the excited state and redox properties of each complex was characterized for the photo- and electrocatalytic production of H2. The oxidation potentials shift anodically from 1 to 3, consistent with a highest occupied molecular orbital (HOMO) with significant metal-ligand mixing, Rh2(δ*)/DPhF(π/nb). In contrast, modest differences in the first two bncn-localized reversible reduction potentials were observed in 1 - 3. The lowest energy metal/ligand-to-ligand charge transfer (1ML-LCT) transition, Rh2(δ*)/DPhF(π/nb) → bncn(π*), shifts from 633 nm in 1 to 553 nm in 2, and the metal-to-ligand charge transfer (1MLCT) Rh2(π*) → bncn(π*) absorption in 3 appears at 462 nm in CH3CN. Although the 3ML-LCT excited state of 2 is shorter lived than that of 1, 2.7 ns as compared to 19 ns, respectively, photocatalytic hydrogen generation is observed for the former upon 595 nm irradiation in the presence of 0.1 M TsOH (p-tolylsulfonic acid) and 0.1 M BNAH (1-benzyl-1,4-dihydronicotinamide). The temperature dependence of the 3ML-LCT lifetimes of 1 and 2 shows the presence of a thermally accessible deactivating state. In addition, the singly reduced intermediate, [2]-, is photoactive and able to generate hydrogen in the presence of TsOH. Importantly, the electrocatalytic currents generated by equimolar concentrations of 1 - 3 in CH3CN are nearly identical, consistent with a mechanism of catalysis that is localized on the bncn ligand and does not require a Rh-H hydride intermediate. This finding can be used to develop earth-abundant first-row transition metal complexes for photo- and electrocatalytic H2 production.

Study on physicochemical properties of catalytically oxidised starches from various botanical sources

Catalytic oxidation of starch with hydrogen peroxide (H2O2) as oxidant has been studied in recent years as a sustainable alternative to conventional sodium hypochlorite (NaOCl). A promising homogeneous catalyst for this is [MnIV2(μ-O)3(tmtacn)2][H2O](CH3COO)2 (Mncat, with tmtacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), an earth abundant metal based catalyst that has been used for commercial industrial applications. We show in this work that oxidation of starches such as (waxy) corn, tapioca, wheat and rice is possible using 0.019 mol% Mncat (with respect to mol anhydroglucose units, or 0.007 wt% when compared to the mass of dry starch) and 1 wt% H2O2 (per dry weight starch), albeit reaching lower degrees of oxidation compared to potato starch. The reasons for the differences in oxidation efficiency and pasting properties were studied. The influence of granule size and lipid content was found to be limited, while crystallinity type and amylose content had an effect on oxidation efficiency. Finally, a unique thermal transition before gelatinisation was observed after oxidation using Mncat/H2O2 which was assigned to solubilisation of the amorphous lamellae of the granules, while the crystalline lamellae were left intact. This showed that oxidation by Mncat primarily takes place in the amorphous sections of the granule. In contrast to oxidation by NaOCl, the Mncat/H2O2 system can produce unique starches which can be heated past the gelatinisation temperature of the native starch.

Copper-Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho-Br Substituted Benzophenones.

The asymmetric hydrogenation of benzophenones, catalyzed by low-activity earth-abundant metal copper, has hitherto remained a challenge due to the substrates equipped with two indistinguishably similar aryl groups. In this study, we demonstrated that the prochiral carbon of the ortho-bromine substrate exhibits the highest electrophilicity and high reactivity among the ortho-halogen substituted benzophenones, as determined by the Fukui function (f+) analysis and hydrogenation reaction. Considering that the enantiodirecting functional bromine group can be easily derivatized and removed in the products, we successfully achieved a green copper-catalyzed asymmetric hydrogenation of ortho-bromine substituted benzophenones. This method yielded a series of chiral benzhydrols with excellent results. The utility of this protocol has been validated through a gram-scale reaction and subsequent product transformations. Hirshfeld partition (IGMH) and energy decomposition analysis (EDA) indicate that the CH···HC multiple attractive dispersion interactions (MADI) effect between the catalyst and substrate enhances the catalyst's activity.

Data-Driven Insights into the Transition-Metal-Catalyzed Asymmetric Hydrogenation of Olefins.

The transition-metal-catalyzed asymmetric hydrogenation of olefins is one of the key transformations with great utility in various industrial applications. The field has been dominated by the use of noble metal catalysts, such as iridium and rhodium. The reactions with the earth-abundant cobalt metal have increased only in recent years. In this work, we analyze the large amount of literature data available on iridium- and rhodium-catalyzed asymmetric hydrogenation. The limited data on reactions using Co catalysts are then examined in the context of Ir and Rh to obtain a better understanding of the reactivity pattern. A detailed data-driven study of the types of olefins, ligands, and reaction conditions such as solvent, temperature, and pressure is carried out. Our analysis provides an understanding of the literature trends and demonstrates that only a few olefin-ligand combinations or reaction conditions are frequently used. The knowledge of this bias in the literature data toward a certain group of substrates or reaction conditions can be useful for practitioners to design new reaction data sets that are suitable to obtain meaningful predictions from machine-learning models.

From Precious to Earth-Abundant Metallic Nanoparticles: A Trend of Interband Transitions in Photocatalyzed Nitrobenzene Reduction.

Metallic nanoparticles have been demonstrated to be versatile photocatalysts, as exemplified by those made from noble and precious metals. Transitioning from precious to earth-abundant metals for sustainable photocatalysis requires benchmarking their catalytic performance. In this work, we attempt to compare the photocatalytic activities of Au, Pd, and Co-B nanoparticles in the reduction of nitrobenzene by hydrazine. Despite their different morphologies and surface structures, Co-B nanoparticles offer the highest catalytic enhancement when comparing their reaction rates under irradiation to those under nonirradiation conditions. The trend of improved photocatalytic performance when transitioning from Au to Pd, and then to Co-B, can be explained by the nature of their d-band positions and corresponding hot carriers photogenerated from interband transitions.

Synergistic design of processable Nb2O5-TiO2 bilayer nanoarchitectonics: enabling high coloration efficiency and superior stability in dual-band electrochromic energy storage

This paper introduces a proof of concept for a dual-band electrochromic (EC) device to modulate solar light transmission across visible and near-infrared regions selectively. EC materials based on ion insertion/extraction mechanisms also present the possibility for energy storage, widening its functionality to the supercapacitor platform. The bi-functional performance of dual-band radiation control and energy storage was achieved by exploiting two earth-abundant metal oxides that could absorb two different spectral regions when electrochemically charged. The bilayer structure was prepared using a one-step hydrothermal method, which produced Nb2O5-TiO2 bilayer on fluorine-doped tin oxide (FTO) conducting glass substrates. The nano-dimensions of the active materials endorse the development of high-transparency thin film under open circuit conditions. The variations in the TiO2 annealing temperature influence the crystallinity and surface morphology of the thin films, which influence the performance of dual-band EC energy storage. The well-optimized NT-500 sample facilitated exclusive electron-charge transport, producing excellent electrochemical performance in dual-band EC and energy storage. A large optical modulation of 80.4 % and 89.8 % at 600 nm and 800 nm (near-infrared) was achieved with an enhanced areal capacitance of 88.1 mF/cm2 and excellent cycling stability after continuous coloring/bleaching cycles for 18,000 s. This paper presents a prototype bi-functional device based on NT-500, which showed independent control and modulation of visible and near-infrared transmittance. Notably, the device retained excellent energy storage performance alongside its advanced optical functionalities. This bilayer nanostructure capitalizes on the inherent electrochemical properties of both materials and introduces novel features that can potentially revolutionize the platform of EC-energy storage.