Non-noble Catalysts Research Articles

NiP2 as an efficient non-noble metal cathode catalyst for enhanced hydrogen isotope separation in proton exchange membrane water electrolysis

Proton exchange membrane (PEM) water electrolysis is crucial for efficient hydrogen isotope separation (HIS) in liquid water. However, current cathode catalysts like platinum (Pt) suffer from scarcity and limited HIS performance. To overcome this challenge, we propose a simple and effective approach involving the synthesis of highly dispersed NiP2 nanoparticles supported on carbon (NiP2/C) through a solid-phase phosphidation reaction, and for the first time report its enhanced HIS performance as the cathode catalyst in PEM electrolyzer. The NiP2/C catalyst demonstrates excellent catalytic properties as a cathode catalyst for hydrogen evolution reaction (HER) in an acidic electrolyte, achieving low overpotential of only 157 mV at 10 mA/cm2 and Tafel slope of 95.6 mV/dec. Meticulous investigations and density functional theory (DFT) calculations reveal the intrinsic factors behind its performance. Furthermore, DFT calculations predict the HIS performance of both NiP2/C and Ni/C catalysts, revealing the advantages of NiP2/C over Ni/C. Experimental results obtained in practical PEM water electrolysis validate these predictions, as NiP2/C exhibits an impressive separation factor α of 6.36, nearly twice that of the Pt/C catalyst. Moreover, NiP2/C demonstrates reliable and consistent HIS performance during a 100-hour PEM electrolysis process. Importantly, our calculation model for deuterium enrichment in liquid water reveals that catalysts with higher separation factors α show faster deuterium enrichment and higher deuterium recovery rates. The utilization of NiP2/C as a non-noble metal cathode catalyst holds great promise for efficient and sustainable hydrogen isotope separation, addressing the limitations of precious metal catalysts and advancing clean energy technologies.

Modulation of electronic structure of Ni3S2 via Fe and Mo co-doping to enhance the bifunctional electrocatalytic activities for HER and OER

Heazlewoodite nickel sulfide (Ni3S2) is advocated as a promising nonnoble catalyst for electrochemical water splitting because of its unique structure configuration and high conductivity. However, the low active sites and strong sulfur–hydrogen bonds (S–Hads) formed on Ni3S2 surface greatly inhibit the desorption of Hads and reduce the hydrogen and oxygen evolution reaction (HER and OER) activity. Doping is a valid strategy to stimulate the intrinsic catalytic activity of pristine Ni3S2 via modifying the active site. Herein, the Ni foam supported Fe and Mo co-doped Ni3S2 electrocatalysts (Fe-MoS2/Ni3S2@NF) have been constructed using Keplerate polyoxomolybdate {Mo72F30} as precursor through a facile hydrothermal process. Experimental results certificate that Fe and Mo co-doping can effectively tune the local electronic structure, facilitate the interfacial electron transfer, and improve the intrinsic activity. Consequently, the Fe-MoS2/Ni3S2@NF display more excellent HER and OER activity than MoS2/Ni3S2@NF and bare Ni3S2@NF by delivering the 10 and 50 mA cm−2 current densities at ultra-low overpotentials of 74/175 and 80/160 mV for HER and OER. Moreover, when coupled in an alkaline electrolyzer, Fe-MoS2/Ni3S2@NF approached the current of 10 mA cm−2 under a cell voltage of 1.60 V and exhibit excellent stability. The strategy to realize tunable catalytic behaviors via foreign metal doping provides a new avenue to optimize the water splitting catalysts.

Efficient and Durable Oxidation Removal of Formaldehyde over Layered Double Hydroxide Catalysts at Room Temperature.

Room temperature catalytic oxidation (RTCO) using non-noble metals has emerged as a highly promising technique for removal of formaldehyde (HCHO) under ambient conditions; however, non-noble catalysts still face the challenges related to poor water resistance and low stability under harsh conditions. In this study, we synthesized a series of layered double hydroxides (LDHs) incorporating various dual metals (MgAl, ZnAl, NiAl, NiFe, and NiTi) for formaldehyde oxidation at ambient temperature. Among the synthesized catalysts, the NiTi-LDH catalyst showed an HCHO removal efficiency and CO2 yield close to 100.0%, and exceptional water resistance and chemical stability on running 1300 min. The abundant hydroxyl groups in LDHs directly bonded with HCHO, leading to the production of CO2 and H2O, thus inhibiting the formation of CO, even in the absence of O2 and H2O. The coexistence of O2 effectively reduced the reaction barrier for H2O molecule dissociation, facilitating the formation of hydroxyl groups and their subsequent backfill on the catalyst surface. The mechanisms underlying the involvement and regeneration of hydroxyl groups in room temperature oxidation of formaldehyde were elucidated with the combined in situ DRIFTS, HCHO-TPD-MS, and DFT calculations. This work not only demonstrates the potential of LDH catalysts in environmental applications but also advances the understanding of the fundamental processes involved in room temperature oxidation of formaldehyde.

Structural optimization and electrocatalytic hydrogen production performance of carbon-based composites: A mini-review

The energy demand has increased significantly in recent years and it is urgent to develop a renewable energy system that is highly efficient and non-noble metal-based. Hydrogen energy is an environmentally friendly energy source with abundant resources, which can be used to solve the problem of high energy demand without greenhouse gas emissions. However, the development of catalysts for hydrogen production technology by electrolysis of water is slow, mainly due to the complexity of the electrolysis hydrogen generation process, low hydrogen production efficiency, weak electrode material activity and high cost. Among the non-noble metal-based catalysts, carbon-based materials have high conductivity, tunable chemical bonding, and easily modified morphology, making them beneficial to achieving efficient hydrogen production, though pure carbon composites suffer from few surface-active sites and unmoderated hydrogen bonding energy, which need to be further optimized. The principle of electrocatalytic hydrogen production from the perspectives of reaction thermodynamics and kinetics is analyzed and discussed in this paper. Thermodynamics of electrocatalytic hydrogen production is reflected by the Gibbs free energy of hydrogen adsorption (ΔGH*) and electrode potential (E). Reaction kinetics of the electrocatalytic hydrogen production process are reflected by overpotential, Tafel slope and exchange current density. Structural optimization methods of carbon-based composite materials and hydrogen production performance after structural optimization are also summarized. Structural optimization methods of carbon-based composite materials mainly include introducing active sites, improving conductivity, increasing specific surface area and introducing self-supporting materials. Finally, prospects are proposed for the development direction and existing problems of electrocatalytic hydrogen production performance of carbon-based composites.

Bimetallic-doped three-dimensional carbon skeleton porous material as efficient catalysts for oxygen reduction reaction

The slowness of the oxygen reduction reaction (ORR) kinetics of the fuel cell cathode has terrifically inhibited its development process. Now it is of considerable importance to research low-cost, multi-defect, high-performance non-noble metal ORR catalysts. Specifically, CuO nanosheets are grown in situ on ZIF-8 to form a composite material (zif-8@CuO), and then undergo a high-temperature carbonization process. Finally, the Zn-Cu codoped composite material Zn-xCu-N/C with a porous structure supported by a three-dimensional carbon skeleton can be obtained. The material has a 3D carbon skeleton support and a rich pore structure, which can expose more active sites. The combination of bimetallic Zn and Cu with carbon materials also increases the overall stability and conductivity of the material, which is beneficial to improvement of catalytic performance. The electrochemical performance test results show that the onset potential and half-wave potential of the Zn-0.1Cu-N/C material are 0.889 V and 0.803 V respectively, with a low Tafel slope of 62 mV dec−1 and excellent long-term stability. After 10000 cycles, the ORR curve only changed 18 mV, while the carbon skeleton can still maintain unchanged.

Strategic regulation of nitrogen-containing intermediates for enhanced nitrate reduction over Co3O4/SiC catalyst having multiple active centers

Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction (NO3RR) is crucial for the enhancement of reaction efficiency. However, it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst. Here, a family of n%-Co3O4/SiC (n = 5, 8, 12, 20) catalysts with a delicate percentage of Co2+ and Co3+ were prepared for NO3RR. We found that Co3+ primarily acts as the active site for NO3− reduction to NO2−, while Co2+ is responsible for the conversion of NO2− to NH3. Moreover, the conversion of these intermediates over the active sites is autonomous and separately controllable. Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia. Combining the experimental studies and density functional theory (DFT) calculations, it is discovered the pathway (*NHO→*NHOH→*NH2OH→*NH2→*NH3) is more favorable due to the lower ΔG value (0.25 eV) for the rate-limiting step (*NO→*NHO). The NH3 yield rate of 8%-Co3O4/SiC reached 1.08 mmol/(cm2 h) with a Faradaic efficiency of 96.4% at −0.89 V versus the reversible hydrogen electrode (RHE), surpassing those of most reported non-noble NO3RR catalysts. This strategy not only provides an efficient catalyst for NO3RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites, thereby presenting a new approach to enhance the efficiency of intricate reactions.

Porous Ruthenium-Tungsten-Zinc Nanocages for Efficient Electrocatalytic Hydrogen Oxidation Reaction in Alkali.

With the rapid development of anion exchange membrane technology and the availability of high-performance non-noble metal cathode catalysts in alkaline media, the commercialization of anion exchange membrane fuel cells has become feasible. Currently, anode materials for alkaline anion-exchange membrane fuel cells still rely on platinum-based catalysts, posing a challenge to the development of efficient low-Pt or Pt-free catalysts. Low-cost ruthenium-based anodes are being considered as alternatives to platinum. However, they still suffer from stability issues and strong oxophilicity. Here, we employ a metal-organic framework compound as a template to construct three-dimensional porous ruthenium-tungsten-zinc nanocages via solvothermal and high-temperature pyrolysis methods. The experimental results demonstrate that this porous ruthenium-tungsten-zinc nanocage with an electrochemical surface area of 116 m2 g-1 exhibits excellent catalytic activity for hydrogen oxidation reaction in alkali, with a kinetic density 1.82 times and a mass activity 8.18 times higher than that of commercial Pt/C, and a good catalytic stability, showing no obvious degradation of the current density after continuous operation for 10,000 s. These findings suggest that the developed catalyst holds promise for use in alkaline anion-exchange membrane fuel cells.

Construction of Fe-based amorphous active surface microenvironment and its synergistic Fenton-like treatment of organic pollutants

Fe-based amorphous materials with the superiorities of high efficiency and low Fe sludge secondary pollution can be seen as a potential alternative to Fenton catalysts. However, catalyst deactivation on the catalyst surface hinders the sustainability of high degradation activity. In this study, the degradation capabilities of FeBCCr amorphous alloys in methylene blue (MB) solution by Fenton-like method were explored. The optimum (Fe81B10C9)99Cr1 ribbon with a more uniform Fe3B-like amorphous structure, which exhibits a thin and easily-peeled oxide layer, provides unique dynamic self-renewing to obtain excellent efficiency and recyclability. The degradation rate with 0.05 g/L (Fe81B10C9)99Cr1 ribbon reached 0.248 min−1 and the recyclability reached a charming record of over 90 times with a dosage of 0.1 g ribbon. The activation energy of (Fe81B10C9)99Cr1 ribbon (12.97 kJ mol−1) was found to be superior to that of most metallic catalysts. More importantly, the boron-rich film in the interfacial region can both retard further oxidation of iron and provides a channel for electron transmission, which can contribute to the persistence of a highly active microenvironment with more Fe(Ⅱ) sites and highly utilization of H2O2. The limit segmentation method has verified the good performance in both heterogeneous and homogeneous reactions. This study introduces a strategy for designing high-performance non-noble metallic catalysts through cluster structure regulation, which provides a novel Fenton-like amorphous material with long recyclability of high degradation activity for water remediation.

MIL-101(Fe)-derivatized cathode as an efficient oxygen electrocatalyst for rechargeable Zn-air battery

The exploration of multifunctional electrocatalysts with cost-effective and high kinetic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is crucial for the development of advanced energy conversion and storage equipment. Herein, a novel hierarchical mesoporous/macropores MIL-101(Fe) derivative carbon catalyst material was prepared by a simple molten ZnCl2-assisted synthesis route. Specifically, 1H-benzotriazole (BTA) organic ligands were intentionally introduced as nitrogen sources in order to induce the formation of charge-rich regions through an electronegative nitrogen doping control strategy, and most importantly, the lone pair electron-rich nature of element N could facilitate the separation and anchoring of iron species enchanted the utilization rate of active sites. Because of these properties, the as-prepared catalyst (denoted as FeSACs/NxC) possesses unrivalled bifunction electrocatalytic activity and durability for the ORR and OER. The FeSACs/N1.25C as working electrode exhibits a quite satisfactory electrochemical performance for the ORR (half-wave potential of 0.82 V) and OER (a small overpotential of 302 mV at 10 mA cm−2) in the classic three-electrode configuration. Moreover, the FeSACs/N1.25C-based air cathode imparts encouraging performance in a rechargeable Zn–air battery prototype with an open-circuit voltage of 1.45 V, a specific capacity of 792.16 mAh g−1, an energy density of 871.38 Wh kg−1, and excellent stability for 120 h. This work has opened the way for the development of low-cost, fast kinetic and stable non-noble metal multifunctional catalysts.

Bimetallic Nitride Ni3Mo3N Microrods with Abundant Catalytic Sites Used as Efficient Electrocatalysts for Hydrogen Evolution Reaction

The importance of efficient and stable hydrogen evolution reaction (HER) electrocatalysts for hydrogen production in alkaline conditions to energy crisis resolution and environmental pollution is immense. In general, the quantity of catalytic sites in the electrocatalyst limits the current density of HER. In response to such problems, the bimetallic effect of non-noble bimetallic nitrides has been shown to regulate the corresponding catalytic sites. Here, a microrod-like non-noble bimetallic nitride catalyst with Ni3Mo3N microrods uniformly modified on nickel foam was synthesized by hydrothermal and nitriding processes. The catalyst showed high catalytic activity for HER in 1 M KOH solution. The overpotential was only 28 mV at a current density of 10 mA·cm−2, demonstrating exceptional electrochemical performance. Furthermore, it exhibited remarkable long-term stability under the same current density. This work will open up a low-cost and simple way for the synthesis of bimetallic nitrides as functional electrode materials for HER and electrochemical detection.

CoFe(OH)x-Co3O4/NF as highly efficient electrocatalyst for oxygen evolution and urea oxidation reactions at high current densities

The advancement of an affordable and highly effective catalyst for the oxygen evolution reaction (OER) is essential to enhance the performance of overall water splitting (OWS). Here, we report a highly efficient nickel foam (NF)-supported CoFe(OH)x-Co3O4/NF heterostructure catalyst for OER. The CoFe(OH)x-Co3O4/NF heterostructure catalyst contain amorphous phase CoFe(OH)x and crystalline Co3O4, and the synergistic interaction between the two different phases reduces the charge transfer resistance, accelerates the kinetic processes of electrocatalysis and makes the catalysts exhibit excellent catalytic performance. In 1.0 M KOH solution, an overpotential (η) of merely 262 mV is needed to attain a current density of 100 mA cm−2. Even at high current densities demanded for commercial applications, the overpotentials remain very low (η500 = 291 mV, η1000 = 319 mV). The catalytic activity of CoFe(OH)x-Co3O4/NF has exceeded that of most non-noble metal OER catalysts documented in the literature. Furthermore, the CoFe(OH)x-Co3O4/NF catalyst demonstrates superior catalytic stability to OER, with only a 23 mV potential increase after 24 h of stability testing at a high current density of 500 mA cm−2. Owing to the heterostructure, the CoFe(OH)x-Co3O4/NF catalyst also exhibits excellent catalytic performance for the urea oxidation reaction (UOR), and the use of UOR instead of OER at the anode of OWS significantly reduces the cell voltage, thereby reducing the electrolytic energy consumption. The findings in this work offer precious insights into the design of OWS anode catalysts and their important applications in industrial water electrolysis. These insights are crucial for advancing the development of highly efficient and sustainable water electrolysis processes, which is essential for the production of green hydrogen and other valuable chemicals.

Investigation of Co3O4 modified carbon black as an efficient non-noble metal oxygen reduction catalyst in self-driven phosphorus recovery systems

Phosphorus and nitrogen recovery from urine in the form of struvite via a Mg-air fuel cell (MAFC) platform has previously been reported as a promising approach to achieving sustainable development goals. However, the applicability of this technology has been hindered by the expensive cathodic catalyst, i.e., Pt/C. In this study, an efficient and cost-effective non-precious metal catalyst, the Co3O4 doped carbon black (CB-ZIF-900), was developed to maximize nitrogen and phosphate recovery from urine while reducing investment costs. CB-ZIF-900 exhibited an oxygen reduction reaction current density of 2.95 mA cm−2 and an electron transfer number between 3.7 and 3.9 in urine solution, which approached those of commercial Pt/C at the same testing conditions. Using the MAFC, over 99 % of phosphorus was removed from urine, and >95 % of phosphorus was recovered in the precipitates. Stable phosphorus removal efficiency and precipitates composition were observed over five consecutive batch experiments. Furthermore, the MAFC with CB-ZIF-900 exhibited a maximum power density of 594.89 W m−3, surpassing that with commercial Pt/C by 9.3 %. These findings underscore the utility of the highly efficient and cost-effective CB-ZIF-900 for advancing the scalability and widespread applications of self-driven phosphorus recovery systems.

FeNi alloy embedded in three-dimensional nitrogen-doped porous carbon as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries

Iron‑nickel (FeNi) alloy is one of the efficient bifunctional oxygen electrocatalysts for zinc-air batteries (ZABs). However, FeNi alloy nanoparticles prepared by traditional synthesis strategies are easy to agglomerate and have non-uniform sizes, which is not conducive to the improvement of catalytic activity and stability. Here, we have successfully encapsulated two different kinds of nitrogen-rich metal phthalocyanines (MPcs) in situ doping in zeolitic imidazolate framework (ZIF-8) homogeneously by the “double solvents” method. The ligand nitrogen and macrocyclic structure of MPcs encapsulated in ZIF-8 not only helps metal dispersion and enhances the metal-ligand‑nitrogen (M-Nx) structure, but also enhances the graphitisation of three-dimensional (3D) porous carbon after pyrolysis. Thus, a FeNi alloy uniformly embedded in 3D nitrogen-doped porous carbon materials (FeNi@NC) was constructed in the subsequent pyrolysis process and used as an efficient bifunctional oxygen reduction/evolution (ORR/OER) electrocatalyst for rechargeable ZABs. Impressively, the FeNi@NC catalyst carries high half-wave potential (0.850 V) in ORR and the low overpotential (291 mV) in OER, significantly better than Pt/C (0.830 V) and RuO2 (307 mV), respectively. In addition, the rechargeable ZAB assembled with FeNi@NC air cathode has a specific capacity of 649 mW cm−2 and shows no significant degradation after 240 h of charging and discharging cycles. This study provides a new design idea for the manufacture of carbon-supported non-noble metal alloy catalysts with bifunctional oxygen catalytic activity, and verifies the feasibility of regulating the composition of non-noble metals to construct a rechargeable ZABs with excellent performance.

Highly Active W2C-Based Composites for the HER in Alkaline Solution: the Role of Surface Oxide Species.

The hydrogen evolution reaction (HER) is a crucial electrochemical process for the proposed hydrogen economy since it has the potential to provide pure hydrogen for fuel cells. Nowadays, hydrogen electroproduction is considerably expensive, so promoting the development of new non-noble catalysts for the cathode of alkaline electrolyzers appears as a suitable way to reduce the costs of this technology. In this sense, a series of tungsten-based carbide materials have been synthesized by the urea-glass route as candidates to improve the HER in alkaline media. Moreover, two different pyridinium-based ionic liquids were employed to modify the surface of the carbide grains and control the amount and nature of their surface species. The main results indicate that the catalyst surface composition is modified in the hybrid materials, which are then distinguished by the appearance of tungsten suboxide structures. This implies the action of ionic liquids as reducing agents. Consequently, differential electrochemical mass spectrometry (DEMS) is used to precisely determine the onset potentials and rate-determining steps (RDS) for the HER in alkaline media. Remarkably, the modified surfaces show high catalytic performance (overpotentials between 45 and 60 mV) and RDS changes from Heyrovsky-Volmer to Heyrovsky as the surface oxide structures get reduced. H2O molecule reduction is then faster at tungsten suboxide, which allows the formation of the adsorbed hydrogen at the surface, boosting the catalytic activity and the kinetics of the alkaline HER.

Rational Design of Non-Noble Metal Single-Atom Catalysts in Lithium-Sulfur Batteries through First Principles Calculations.

Lithium-sulfur (Li-S) batteries with a high theoretical energy density of 2600 Wh·kg-1 are hindered by challenges such as low S conductivity, the polysulfide shuttle effect, low S reduction conversion rate, and sluggish Li2S oxidation kinetics. Herein, single-atom non-noble metal catalysts (SACs) loaded on two-dimensional (2D) vanadium disulfide (VS2) as the potential host materials for the cathode in Li-S batteries were investigated systematically by using first-principles calculations. Based on the comparisons of structural stability, the ability to immobilize sulfur, electrochemical reactivity, and the kinetics of Li2S oxidation decomposition between these non-noble metal catalysts and noble metal candidates, Nb@VS2 and Ta@VS2 were identified as the potential candidates of SACs with the decomposition energy barriers for Li2S of 0.395 eV (Nb@VS2) and of 0.162 eV (Ta@VS2), respectively. This study also identified an exothermic reaction for Nb@VS2 and the Gibbs free energy of 0.218 eV for Ta@VS2. Furthermore, the adsorption and catalytic mechanisms of the VS2-based SACs in the reactions were elucidated, presenting a universal case demonstrating the use of unconventional graphene-based SACs in Li-S batteries. This study presents a universal surface regulation strategy for transition metal dichalcogenides to enhance their performance as host materials in Li-S batteries.

Non-noble metals coordinated covalent organic frameworks as oxidase-like biocatalysts for light-responsive biomarker sensing

Metal-based enzyme-mimetic biocatalysts exhibit much better enzyme-like activity than metal-free biocatalysts. At the same time, both non-noble and noble metal-based catalysts have been proven to exhibit good biocatalytic activity. It is a great challenge to find extremely sensitive and adaptable biosensors with biocatalytic activity in biotechnology and medical diagnostics. For performance improvement and cost reduction, the development of non-noble metal-based biocatalysts is still of great significance. Here, we disclose that the covalent organic frameworks (COFs) coordinated by cobalt (Co) or nickel (Ni) with specific oxidase-like (OXD-like) activities can serve as intelligent artificial enzymes for light-augmented biocatalytic sensing of biomarkers. Because of the effects of metallic elements on the band gap adjustment, the Ni–COF exhibited the most efficient, selective, and light-responsive OXD-like biocatalytic activity (Km = 0.91 mM, Vmax = 1.50 μM s−1). Moreover, COFs loading metals show superior light-augmented biocatalytic detection capabilities. Notably, Ni–COF exhibits the most efficient and multifaceted diagnostic activity, including the extremely low limit of detection (LOD): 0.34 μM for glutathione and 0.54 μM for L-cysteine, which enables visual assays for abundant reducibility biomarkers. This study offers a unique and efficient non-noble metal-coordinated COF biocatalyst for high-sensitive and low-cost colorimetric detection. It also provides new insights into the design of non-noble metal elements in COF materials with better enzyme-like activities in biocatalytic and biomedical applications.

Research Advances of Non-Noble Metal Catalysts for Oxygen Evolution Reaction in Acid.

Water splitting is an important way to obtain hydrogen applied in clean energy, which mainly consists of two half-reactions: hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). However, the kinetics of the OER of water splitting, which occurs at the anode, is slow and inefficient, especially in acid. Currently, the main OER catalysts are still based on noble metals, such as Ir and Ru, which are the main active components. Hence, the exploration of new OER catalysts with low cost, high activity, and stability has become a key issue in the research of electrolytic water hydrogen production technology. In this paper, the reaction mechanism of OER in acid was discussed and summarized, and the main methods to improve the activity and stability of non-noble metal OER catalysts were summarized and categorized. Finally, the future prospects of OER catalysts in acid were made to provide a little reference idea for the development of advanced OER catalysts in acid in the future.

Highly Effective Non-Noble MnO2 Catalysts for 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid.

Noble metal-free catalyst or catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid are proposed in this study as a proposal to solve one of the great disadvantages of this reaction of using preferably noble metal-based catalysts. The catalytic activity of six MnO2 crystal structures is studied as alternative. The obtained results showed a strong connection between catalytic activity the type of MnO2 structure organization and redox behavior. Among all tested catalysts, ϵ-MnO2 showed the best performance with an excellent yield of 74 % of 2,5-furandicarboxylic acid at full -hydroxymethylfurfural conversion.

Ammonia-regulated CuCo2O4 spinel oxide embedded in Y zeolite for methanol oxidation

Morphology-controlled synthesis with a tailor-made structure is a promising approach to enhance the catalytic properties of inexpensive spinel oxides as a viable alternative to noble metals. AB2O4 spinel oxides, particularly, have garnered significant attention in mitigating volatile organic compounds (VOCs) emissions. The catalytic performance of these oxides can be improved through the modification of tetrahedrally coordinated A sites. In this study, we present a novel strategy for the preparation of CuCo2O4 spinel oxide nanoparticles embedded on Y zeolite. This involves the co-loading of Cu and Co oxides on Y zeolite, followed by successive treatment with NH3-reduction and re-oxidation. The resulting morphology-confined CuCo2O4 spinel oxides exhibit significantly higher catalytic activities and stabilities for the oxidation of CH3OH compared to their unrestrained counterparts. Our exploration into the in-situ formation of spinel oxides on Y zeolite, along with an investigation into their catalytic oxidation mechanism, lays the foundation for the rational design of non-noble metal oxide VOC catalysts.

Dual-function CoP on nitrogen doped carbon framework with induced interfacial coupling for overall water splitting

Strong interfacial coupling in the hybrid catalysts could enhance catalytic performances. In this work, N, P were co-doped in zeolitic imidazolate framework-67 (ZIF-67) derived Co-based materials (denoted as CoP/NC) via in-situ carbonization and phosphating strategy, which accordingly induced strong interfacial coupling, leading to promote the catalytic activity in overall water splitting. In detail, the CoP/NC-2 presents the overpotential of 98 and 139 mV for hydrogen evolution reaction (HER) in 0.5 M H2SO4 and 1.0 M KOH at 10 mA cm−2, respectively, and 295 mV for oxygen evolution reaction (OER) in 1.0 M KOH at 20 mA cm−2, which is excellent during the non-noble metal-based catalysts. It also achieved a potential of 1.69 V (η20) in the overall water splitting. Density functional theory (DFT) based calculation reveals that the in-situ N, P co-doping induced strong interface coupling, which enhances the interaction in the interface of catalysts and improves electron conduction. More importantly, it contributes to adjusting electronic structure and d-band center, optimizing the adsorption energy for HER and/or OER and improving the kinetics of water splitting reaction. This work sheds new light on the heteroatom doping strategy to construct bifunctional transition metal-based electrocatalyst with boosting electrocatalytic performance in energy conversion application.