Non-noble Metal-based Catalysts Research Articles

Atomically dispersed dual iron and manganese anchored nitrogen doped reduced graphene as robust cathode catalyst for direct methanol fuel cell and aluminium air battery

A noble metal-free atomically dispersed dual metal (Fe and Mn) anchored nitrogen (N)-doped reduced graphene oxide (rGO) is synthesized as a high-performance oxygen reduction reaction (ORR) electrocatalyst for alkaline direct methanol fuel cell and aluminium-air battery (AAB). The as-synthesized FeMn-NrGO catalyst exhibits a half-wave potential of 0.84 V for ORR and a low onset potential of 0.96 Vvs (RHE). The theoretical study reveals that the synergetic coupling of Mn and Fe with pyridinic and pyrrolic nitrogen weakening adsorption bond strength of the O* intermediates to the active site of the catalyst, thereby improving the for ORR performance. The synthesized Fe3Mn1-NrGO cathode catalyst assembled alkaline direct methanol fuel cell (DMFC) demonstrates a peak power density of 65 mW/cm2 extending an effective strategy to enhance the ORR kinetics of the non-noble metal-based catalyst for fuel cell application. Furthermore, the synthesized Fe3Mn1-NrGO also exhibits excellent ORR activity in 3.5 wt% NaCl solution and demonstrates a peak power density of 11.2 mW/cm2 aqueous NaCl electrolyte-based AAB system.

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.

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.

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.

Isolated Ni sites anchored on zeolites for direct synthesis of acetic acid from methane oxidative carbonylation

Direct conversion of methane to acetic acid with high activity and selectivity over non-noble metal-based catalysts under mild reaction conditions remains a grand challenge. Specifically, 1.2Ni-ZSM-5 with 88.9 % isolated Ni sites achieved a high acetic acid yield of 2920 μmol/gcat. and a remarkable selectivity up to 82.3 % from methane oxidative carbonylation. Combined with high angle annular dark field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy analyses, it was revealed that the isolated Ni species with Ni-O6 moieties anchored in the micropores of ZSM-5 were suggested to be the active sites. The isotopic labeling experiments and monitoring of reaction intermediates demonstrated that CH3COOH was formed via the direct coupling of methyl radicals and carbon monoxide molecules. This work suggests that the well-designed Ni sites can promote the transformation of CH4 to C2+ oxygenates instead of traditional C1 oxygenates as main products.

Superaerophobic/Superhydrophilic Multidimensional Electrode System for High-Current-Density Water Electrolysis.

Water electrolysis is emerging as a promising renewable-energy technology for the green production of hydrogen, which is a representative and reliable clean energy source. From economical and industrial perspectives, the development of earth-abundant non-noble metal-based and bifunctional catalysts, which can simultaneously exhibit high catalytic activities and stabilities for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), is critical; however, to date, these types of catalysts have not been constructed, particularly, for high-current-density water electrolysis at the industrial level. This study developed a heterostructured zero-dimensional (0D)-one-dimensional (1D) PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF)-Ni3S2 as a self-supported catalytic electrode via interface and morphology engineering. This unique heterodimensional nanostructure of the PBSCF-Ni3S2 system demonstrates superaerophobic/superhydrophilic features and maximizes the exposure of the highly active heterointerface, endowing the PBSCF-Ni3S2 electrode with outstanding electrocatalytic performances in both HER and OER and exceptional operational stability during the overall water electrolysis at high current densities (500 h at 500 mA cm-2). This study provides important insights into the development of catalytic electrodes for efficient and stable large-scale hydrogen production systems.

Catalytic CO Oxidation on the Cu+-Ov-Ce3+ Interface Constructed by an Electrospinning Method for Enhanced CO Adsorption at Low Temperature.

It is crucial to eliminate CO emissions using non-noble catalysts. Cu-based catalysts have been widely applied in CO oxidation, but their activity and stability at low temperatures are still challenging. This study reports the preparation and application of an efficient copper-doped ceria electrospun fiber catalyst prepared by a facile electrospinning method. The obtained 10Cu-Ce fiber catalyst achieved complete CO oxidation at a temperature as low as 90 °C. However, a reference 10Cu/Ce catalyst prepared by the impregnation method needed 110 °C to achieve complete CO oxidation under identical reaction conditions. Asymmetric oxygen vacancies (ASOV) at the interface between copper and cerium were constructed, to effectively absorb gas molecules involved in the reaction, leading to the enhanced oxidation of CO. The exceptional ability of the 10Cu-Ce catalyst to adsorb CO is attributed to its unique structure and surface interaction phase Cu+-Ov-Ce3+, as demonstrated by a series of characterizations and DFT calculations. This novel approach of using electrospinning offers a promising technique for developing low-temperature and non-noble metal-based catalysts.

Non-Noble Metal High-Entropy Alloy-Based Catalytic Electrode for Long-Life Hydrogen Gas Batteries.

The development of efficient, stable, and low-cost bifunctional catalysts for the hydrogen evolution/oxidation reaction (HER/HOR) is critical to promote the application of hydrogen gas batteries in large scale energy storage systems. Here we demonstrate a non-noble metal high-entropy alloy grown on Cu foam (NNM-HEA@CF) as a self-supported catalytic electrode for nickel-hydrogen gas (Ni-H2) batteries. Experimental and theoretical calculation results reveal that the NNM-HEA catalyst greatly facilitates the HER/HOR catalytic process through the optimized electronic structures of the active sites. The assembled Ni-H2 battery with NNM-HEA@CF as the anode shows excellent rate capability and exceptional cycling performance of over 1800 h without capacity decay at an areal capacity of 15 mAh cm-2. Furthermore, a scaled-up Ni-H2 battery fabricated with an extended capacity of 0.45 Ah exhibits a high cell-level energy density of ∼109.3 Wh kg-1. Moreover, its estimated cost reaches as low as ∼107.8 $ kWh-1 based on all key components of electrodes, separator and electrolyte, which is reduced by more than 6 times compared to that of the commercial Pt/C-based Ni-H2 battery. This work provides an approach to develop high-efficiency non-noble metal-based bifunctional catalysts for hydrogen batteries in large-scale energy storage applications.

Le Chatelier’s principle to stabilize intrinsic surface structure of oxygen-evolving catalyst for enabling ultra-high catalytic stability of zinc-air battery and water splitting

Well-designed highly active intrinsic surface structure of a catalyst for oxygen evolution reaction (OER) often faces the problem of corrosion dissolution, which severely deteriorates its catalytic stability, and breaking this activity-stability trade-off has always been a huge and long-term challenge. Herein, we employ Le Chatelier’s principle to address this dissolution problem of the catalyst to maintain its intrinsic surface structure for highly efficient and ultra-stable OER. Taking highly active but susceptible oxygen vacancy-rich Co-W oxide as the model catalyst for alkaline OER, its dissolving kinetics is significantly passivated by introducing homo ions into the electrolyte to regulate the dissolution equilibrium, thus achieving ultralong operating stability without sacrificing its high activity. The theoretical calculations and in-situ experimental results unravel the underlying mechanism of this strategy, that is, the homo ions (tungstate ions) can be preferentially adsorbed on the catalyst surface to construct a local non-corrosive environment, thus effectively stabilizing the well-designed unsaturated active cobalt sites to maintain the intrinsic surface structure of the catalyst and preventing them from being reconstructed or transformed toward the unfavorable direction. Importantly, this strategy is also effective in zinc-air battery and electrolytic water splitting, achieving ultra-stable performance over 1200 h, which is of great importance for promoting the practical applications of low-cost non-noble metal-based catalysts in energy devices.

Graphene Chainmail Shelled Dilute Ni─Cu Alloy for Selective and Robust Aqueous Phase Catalytic Hydrogenation.

Cost-effective non-noble metal-based catalysts for selective hydrogenation with excellent activity, selectivity, and durability are still the holy grail. Herein, an oxygen-doped carbon (OC) chainmail encapsulated dilute Cu-Ni alloy is developed by simple pyrolysis of Cu/Ni-metal-organic framework. The CuNi0.05@OC catalyst displays superior performance for atmospheric pressure transfer hydrogenation of p-chloronitrobenzene and p-nitrophenol, and for hydrogenation of furfural, all in water and with exceptional durability. Comprehensive characterizations confirm the close interactions between the diluted Ni sites, the base Cu, and optimized three-layered graphene chainmail. Theoretical calculations demonstrate that the properly tuned lattice strain and Schottky junction can adjust electron density to facilitate specific adsorption on the active centers, thus enhancing the catalytic activity and selectivity, while the OC shell also offers robust protection. This work provides a simple and environmentally friendly strategy for developing practical heterogeneous catalysts that bring the synergistic effect into play between dilute alloy and functional carbon wrapping.

Laser assisted oxygen vacancy engineering on Fe doped CoO nanoparticles for oxygen evolution at large current density

Exploring cost-effective non-noble metal-based catalysts with high activity and stability is of great significance for energy conversion and storage involving oxygen evolution reaction (OER). Here, we employed a laser irradiation technique to synthesis Fe doped CoO nanoparticles with ultrafine size (≈ 5.4 nm) and abundant oxygen vacancies (Fe-Ov-CoO). The ultrafine size of Fe-Ov-CoO nanoparticles provides more active sites to be exposed. Fe doping and oxygen vacancy promote the intrinsic activity and electron transfer rates of Fe-Ov-CoO, giving rise to high activity and stability catalyst for OER. Fe-Ov-CoO delivers a large current density of 1000 mA cm−2 at an overpotential of 548 mV, which is much better than commercial RuO2. Moreover, Fe-Ov-CoO presents a remarkable long-term stability with negligible degeneration at a high current density of 500 mA cm−2 for 120 h. This work provides a new route to develop OER electrocatalyst with high activity and stability.

Air-stable and reusable porous silica-supported ultrafine Nix-NiO nanoparticles for semi-hydrogenation of alkynes

The practical application of non-noble metal-based hydrogenation catalysts is limited because of their low activity and easy oxidation in air. Here, porous silica-supported ultrafine nickel oxide (NiO) was prepared by calcining an organic–inorganic hybrid 3D nanomaterial that was formed via the Michael addition/Schiff’s base reaction, and hydrolyzation of triethoxysilane. NiO nanoparticles with ca. 2.6 nm diameter was uniformly dispersed and confined in the cogenerated mesoporous SiO2 skeleton, thanks to the coordination between pyrogallol/amino units and Ni2+ ions, and the isolation effect of Si-O-Si network. The as-prepared catalyst featured mesoporous structure and high specific surface area (715 m2/g), and exhibited excellent activity, selectivity and reusability in the semi-hydrogenation of alkynes. Small amount of metallic nickel (Nix-NiO) that formed on the surface of NiO nanoparticles during the semi-hydrogenation acted as the active species, and the moderate adsorption/desorption energies on Nix-NiO facilitated the activity enhancement. Most importantly, it showed constant catalytic activity and selectivity after a long-term storage in air. This work provides a green and feasible strategy, as an alternative to the traditional impregnation method, for the preparation of ultrafine metal-supported catalysts with air-stability and reusability.

A self-supported porous NiMo electrocatalyst to boost the catalytic activity in the hydrogen evolution reaction.

To develop hydrogen energy production and address the issues of global warming, inexpensive, effective, and long-lasting transition metal-based electrocatalysts for the synthesis of hydrogen are crucial. Herein, a porous electrocatalyst NiMo/Ni/NF was successfully constructed by a two-step electrodeposition process, and was used in the hydrogen evolution reaction (HER) of electrocatalytic water decomposition. NiMo nanoparticles were coated on porous Ni/NF grown on nickel foam (NF), leading to a resilient porous structure with enhanced conductivity for efficient charge transfer, as well as distinctive three-dimensional channels for quick electrolyte diffusion and gas release. Notably, the low overpotential (42 mV) and fast kinetics (Tafel slope of 44 mV dec-1) at a current density of 10 mA cm-2 in 1.0 M KOH solution demonstrate the excellent HER activity of the electrode, which was superior to that of recently reported non-noble metal-based catalysts. Additionally, NiMo/Ni/NF showed extraordinary catalytic durability in stability tests at a current density of 10 mA cm-2 for 70 h. The porous structure catalyst and the electrodeposition-electrocatalysis technique examined in this study offer new approaches for the advancement of the electrocatalysis field because of these benefits.

A manganese-based catalyst system for general oxidation of unactivated olefins, alkanes, and alcohols.

Non-noble metal-based catalyst systems consisting of inexpensive manganese salts, picolinic acid and various heterocycles enable epoxidation of the challenging (terminal) unactivated olefins, selective C-H oxidation of unactivated alkanes, and O-H oxidation of secondary alcohols with aqueous hydrogen peroxide. In the presence of the in situ generated optimal manganese catalyst, epoxides are generated with up to 81% yield from alkenes and ketone products with up to 51% yield from unactivated alkanes. This convenient protocol allows the formation of the desired products under ambient conditions (room temperature, 1 bar) by employing only a slight excess of hydrogen peroxide with 2,3-butadione as a sub-stoichiometric additive.

Polyoxometalate-derived electrocatalysts enabling progress in hydrogen evolution reactions.

Platinum-based catalysts exhibit outstanding electrocatalytic performance in the hydrogen evolution reaction (HER). However, platinum-based catalysts face significant challenges due to their rarity and high cost. This paper endeavors to shed light on a promising alternative: polyoxometalate (POM)-based catalysts, which possess significant potential for the synthesis of non-noble metal-based catalysts for the HER. Utilizing POMs as raw materials to assemble POM-derived materials, including POM-derived crystalline materials, metal sulfides, phosphides, carbides, nitrides, and so on, has emerged as an effective approach for the synthesis of hydrogen evolution electrocatalysts. This approach offers advantages in both stability and electrocatalytic performance. This comprehensive review navigates through latest progress in the assembly strategy and HER performance of POM-based crystal materials, alongside discussion on transition metal compounds derived from POMs, such as carbides, phosphides, and sulfides. Besides, future developments in POM-derived electrocatalyst regulation of the electrochemical HER are prospected.

Influence of the catalyst precursor for cobalt on activated carbon applied in ammonia decomposition

Ammonia is a key compound for storing and transporting green hydrogen. However, the efficient release of stored hydrogen through thermocatalytic ammonia decomposition is achievable only at temperatures around 600 °C, particularly with non-noble metal-based catalysts, which prove to be both ecologically and economically more feasible. In this study, electrically conductive activated carbon was selected as the catalyst support, chosen specifically for its suitability in achieving more energy-efficient direct reactor heating through the ohmic resistance of the catalysts. Cobalt salts were wet impregnated on activated carbon investigating the influence of different precursors (cobalt nitrate and cobalt acetate) and pyrolysis temperatures (400 °C and 600 °C) under N2 flow on the cobalt particle size and the incorporation of cobalt into the carbon matrix. TEM imaging and CO-chemisorption revealed well dispersed cobalt particles with sizes below 10 nm for the catalysts synthesized from the cobalt nitrate precursor. On the other hand, cobalt acetate led to about nine times larger Co agglomerates, which were partially detached from the carbon matrix. Moreover, this substantial difference in the Co particle size results in a significantly higher ammonia conversion for cobalt nitrate-based catalysts, achieving 94 % of ammonia conversion at 600 °C. Furthermore, the long-term stability test of the cobalt nitrate-based catalyst resulted in a slight deactivation of only 2 % ammonia conversion at 500 °C.

Heterogeneous Catalysts for Carbon Dioxide Methanation: A View on Catalytic Performance

CO2 methanation offers a promising route for converting CO2 into valuable chemicals and energy fuels at the same time as hydrogen is stored in methane, so the development of suitable catalysts is crucial. In this review, the performance of catalysts for CO2 methanation is presented and discussed, including noble metal-based catalysts and non-noble metal-based catalysts. Among the noble metal-based catalysts (Ru, Rh, and Pd), Ru-based catalysts show the best catalytic performance. In the non-noble metal catalysts, Ni-based catalysts are the best among Ni-, Co-, and Fe-based catalysts. The factors predominantly affecting catalytic performance are the dispersion of the active metal; the synergy of the active metal with support; and the addition of dopants. Further comprehensive investigations into (i) catalytic performance under industrial conditions, (ii) stability over a much longer period and (iii) activity enhancement at low reaction temperatures are anticipated to meet the industrial applications of CO2 methanation.

A general and robust Ni-based nanocatalyst for selective hydrogenation reactions at low temperature and pressure.

Catalytic hydrogenations are important and widely applied processes for the reduction of organic compounds both in academic laboratories and in industry. To perform these reactions in sustainable and practical manner, the development and applicability of non-noble metal-based heterogeneous catalysts is crucial. Here, we report highly active and air-stable nickel nanoparticles supported on mesoporous silica (MCM-41) as a general and selective hydrogenation catalyst. This catalytic system allows for the hydrogenation of carbonyl compounds, nitroarenes, N-heterocycles, and unsaturated carbon─carbon bonds in good to excellent selectivity under very mild conditions (room temperature to 80°C, 2 to 10 bar H2). Furthermore, the optimal nickel/meso-silicon dioxide catalyst is reusable (4 cycles) without loss of its catalytic activity.

Multi-metal catalysts for selective furfural hydrogenation: Toward biomass valorisation

The research presented here focuses on the design of non-noble transition metal-based bimetallic catalysts, prepared via a green sol-gel process (the urea-glass route), which leads to well-defined (in composition and size) and crystalline nanoparticles, with high surface area. The potential of these tailor-made catalysts for biomass-related model reactions is also presented. In particular, carbon supported Ni, Ni3Fe, Ni0.5Fe0.5, Ni0.5Fe0.5/Fe3C and Ni0.35Fe0.65/NiFe2O4 nanoparticles were synthesized and tested as-prepared, with no need for post-synthesis purification, activation, or co-catalysts addition. Results showed that these catalysts are active in the liquid-phase hydrogenation of furfural (FUR), with almost full conversion with Ni° catalyst, at 170 °C after 22 h, under 4 MPa hydrogen pressure, obtaining the highest yield towards tetrahydrofurfuryl alcohol (THFA) of 85%. More interesting, the incorporation of Fe, to form NiFe alloys, modifies the hydrogenating capacity of the catalyst, provoking a change in the selectivity pattern, from tetrahydrofurfuryl alcohol (THFA), obtained as the only product with Ni° nanoparticles, to furfuryl alcohol (FFA). Thus, high FFA and THFA yields can be obtained by modifying the nature of the metallic phase of samples synthesized with the urea-glass route, demonstrating the potential of this methodology for the preparation of active and selective catalysts for liquid-phase FUR hydrogenation.

Edge-rich molybdenum disulfide tailors carbon-chain growth for selective hydrogenation of carbon monoxide to higher alcohols

Selective hydrogenation of carbon monoxide (CO) to higher alcohols (C2+OH) is a promising non-petroleum route for producing high-value chemicals, in which precise regulations of both C-O cleavage and C-C coupling are highly essential but remain great challenges. Herein, we report that highly selective CO hydrogenation to C2-4OH is achieved over a potassium-modified edge-rich molybdenum disulfide (MoS2) catalyst, which delivers a high CO conversion of 17% with a superior C2-4OH selectivity of 45.2% in hydrogenated products at 240 °C and 50 bar, outperforming previously reported non-noble metal-based catalysts under similar conditions. By regulating the relative abundance of edge to basal plane, C2-4OH to methanol selectivity ratio can be overturned from 0.4 to 2.2. Mechanistic studies reveal that sulfur vacancies at MoS2 edges boost carbon-chain growth by facilitating not only C-O cleavage but also C-C coupling, while potassium promotes the desorption of alcohols via electrostatic interaction with hydroxyls, thereby enabling preferential formation of C2-4OH.