Hydrogen Evolution Reaction Research Articles

Effect of cobalt-doped iron oxide as an electrocatalyst for water splitting and photocatalytic hydrogen evolution

Developing cost-effective and efficient electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is a significant challenge for economically viable energy conversion devices, such as electrolyzers, rechargeable metal-air batteries, and regenerative fuel cells. Here, we have synthesized cobalt doped iron oxides (CoFe2O3) with different Co:Fe wt%. Among them, Co[1:3]Fe2O3 catalyst demonstrated outstanding performance and stability positioning it as a standard electrocatalyst for OER and HER, and as a photocatalyst for H2 production. The catalysts were characterized using various techniques, including field emission scanning electron microscopy (FESEM), X-ray diffraction spectroscopy (XRD), and energy dispersive X-ray spectroscopy (EDS) demonstrating successful application in water electrolysis. Specifically, the onset potentials for OER and HER were 1.63 V/RHE and −0.23 V/RHE, respectively. The overpotential (η) required to achieve 10 mA/cm2 for OER (in alkaline medium) and HER (in acidic medium) was 0.44 and −0.3 V/RHE, respectively. Additionally, the developed OER and HER catalyst exhibited high current and potential stability over a 13-hour period. This approach is considered a promising avenue for making water electrolysis for hydrogen (H2) energy viable by minimizing the energy requirements of the electrolytic process. Similarly, the performance of the fabricated catalyst was also examined for the photocatalytic generation of H2 gas in a photo-reactor. Where the highest generation rate of 97.77 mL. (g.min−1) was recorded for Co[1:3]Fe2O3 as a photocatalyst. As a result, the Co[1:3]Fe2O3 catalyst has the potential to function as both a photocatalyst and an electrocatalyst for water splitting.

Sustainable Processing of Ultralow-Cost Petroleum Cokes Into Ultrastable Self-Doped Fe3C@CNT Catalysts for High-Efficiency HER.

Petroleum cokes are largely used as low-cost anodes in aluminum industries and general fuels in cement industries, where large amounts of CO2 are generated. To reduce CO2 release, it is challenging to develop green strategies for processing abundant petroleum cokes into high-value products, because there are abundant hetero-atoms in petroleum cokes. To overcome such issues, a sustainable electrochemical approach is proposed to convert ultralow-cost high sulfur petroleum coke and iron powders into high-efficiency catalysts for hydrogen evolution reaction (HER). During molten-salt electrolysis, raw petroleum cokes are converted into CNTs via heteroatom removal and the catalytic effect of Fe, forming Fe3C nanoparticles on the sulfur and nitrogen co-dopped carbon nanotubes (Fe3C@S, N-CNTs). The electrochemical reaction analysis using the continuum model suggested that the rate-determining step referred to the slow transport of mobile ions inside the porous cathode. Because the self-doped S and N atoms massively alleviated the energy barrier for H* absorption and H2 desorption (i.e., promoting HER kinetics), the as-prepared Fe3C@S, N-CNTs exhibited low overpotentials at 10mAcm-2 in acidic (96mV) and alkaline (106mV) solutions with ultralong-term duration (200h). This study offers a sustainable approach to convert ultralow-cost petroleum cokes into ultrastable catalysts for high-efficiency HER.

3D printer fabrication of boron doped Cu-MWCNT/PLA electrodes: Investigation of its efficiency in electrocatalytic hydrogen production

In this study, three-dimensional (3D) electrodes based on MWCNT-Cu/PLA with high electrocatalytic efficiency, large surface area and different amounts of nano‑boron doped MWCNT-Cu/PLA were fabricated using Fused Granular Fabrication (FGF) method with a 3D printer. When FE-SEM images are examined, MWCNT fibers and copper particles are seen more clearly on the surface due to the formation of more dense conductive networks between the conductive carbon fibers trapped in the PLA structure due to the increasing amount of boron. When XRD results are examined, it is observed that the characteristic peaks belonging to the face-centered cubic structure of Cu are dominant and the crystal size increases as MWCNT addition and boron doping increase. When Raman spectra were analyzed to investigate the internal structural changes of MWCNTs, three characteristic bands corresponding to the D band (defect), G band (graphite band) and G' band (D overtone) of MWCNTs were determined and it was observed that the ID/IG ratio decreased with increasing boron doping compared to MWCNT-Cu/PLA electrode. The B1s spectrum of the 3D 0.8B@MWCNT-Cu/PLA electrode confirmed the presence of boron with the peak corresponding to B@C bonds at 191.2 eV. The obtained 3D electrocatalysts were used as cathodes in an electrolysis cell in aqueous solution containing 1 M KOH and their catalytic efficiency in hydrogen evolution reaction (HER) was tested. In order to increase the activity of the 3D electrodes, unlike the literature, they were activated by electrochemical activation process without using organic solvent and HER measurements of the activated electrodes were performed. Before activation, the charge transfer resistance (Rct) value of the Cu/PLA electrode, which was 6219.00 Ω cm−2, decreased to 681.90 Ω cm−2 after 5 % MWCNT doping. It is seen that with boron doping, a greater decrease in Rct value is realized, reaching values of 66.50–74.56 Ω cm−2. The cathodic Tafel slopes show that the Volmer reaction is the rate-determining step for HER and the rate-determining step is the electrochemical adsorption of hydrogen on the metal surface. In addition, energy efficiency tests of the 3D electrodes in HER were also performed and electrochemically active surface areas were determined. Thus, this study has taken an important step toward using 3D electrocatalysts, which are produced with more cost and more flexible designs, unlike previous production techniques, for hydrogen energy production.

Polyoxometalate‐Derived Photocatalysts Enabling Progress in Hydrogen Evolution Reactions

AbstractPhotocatalytic water splitting is capable of converting abundant solar energy into environmentally friendly and renewable chemical energy, presenting a promising solution to alleviate the energy crisis and combat environmental pollution. The development of high‐performance photocatalysts is crucial for significantly improving the efficiency of the hydrogen evolution reaction (HER) involved. Polyoxometalate (POM)‐derived materials, known for their tunable compositions, diverse structures, electron storage/release capabilities, as well as quasi‐semiconductor photochemical properties, serve as highly efficient catalysts in sustainable photosynthesis. This comprehensive review navigates the latest advancements in the assembly strategies and HER performance of POM‐based crystalline materials. It also discusses the composite materials formed by infiltrating POM into metal‐organic frameworks (MOF) and examines the roles of transition metal compounds derived from polyoxometalates, such as sulfides and carbides, in photocatalytic HER. Emphasis is placed on the prospects for the future development of POM‐based compounds as photocatalysts, along with several strategies and outlooks that could facilitate their progress. POM‐derived materials are believed to have significant potential to enhance hydrogen production efficiency while maintaining thermal stability in HER processes.

A strongly coupled 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure for efficient electrocatalytic hydrogen evolution at high current densities.

Developing efficient and durable non-noble metal electrocatalysts for high current-density hydrogen evolution reactions (HER) is a pressing requirement for commercial industrial electrolyzers. In this study, a vertical 1T'-ReSe2@2H-MoSe2 van der Waals heterostructure was developed through interface engineering to enhance the advantages of each component and expose numerous active sites. Experimental investigations and density functional theorycalculations demonstrate significant electronic coupling at the interface between 1T'-ReSe2 and 2H-MoSe2, with suitable Gibbs free energy for hydrogen adsorption. The 1T'-ReSe2@2H-MoSe2 heterostructure catalyst achieves high current density HER with low overpotentials of 191 mV to generate up to 800 mA/cm2 in 0.5 M H2SO4, outperforming commercial 5% Pt/C catalysts. Moreover, this catalyst exhibits rapid reaction kinetics and long-term durability, illustrating a successful approach to designing efficient heterostructure electrocatalysts for hydrogen production through interface engineering.

A Supramolecular‐Nanocage‐Based Framework Stabilized by π‐π Stacking Interactions with Enhanced Photocatalysis

Abstractπ frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π‐π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular‐nanocage‐based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π‐π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π‐2). π‐2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π‐2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co‐catalyst, the hydrogen evolution rate reaches a record‐high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π‐2 to the highly active Pt upon illumination. π‐2 represents the unique stable supramolecular‐cage‐based π framework with excellent photocatalytic activity.

C60 Fullerene‐Induced Reduction of Metal Ions: Synthesis of C60‐Metal Cluster Heterostructures with High Electrocatalytic Hydrogen‐Evolution Performance

AbstractMetal clusters, due to their small dimensions, contain a high proportion of surface atoms, thus possessing a significantly improved catalytic activity compared with their bulk counterparts and nanoparticles. Defective and modified carbon supports are effective in stabilizing metal clusters, however, the synthesis of isolated metal clusters still requires multiple steps and harsh conditions. Herein, we develop a C60 fullerene‐driven spontaneous metal deposition process, where C60 serves as both a reductant and an anchor, to achieve uniform metal (Rh, Ir, Pt, Pd, Au and Ru) clusters without the need for any defects or functional groups on C60. Density functional theory calculations reveal that C60 possesses multiple strong metal adsorption sites, which favors stable and uniform deposition of metal atoms. In addition, owing to the electron‐withdrawing properties of C60, the electronic structures of metal clusters are effectively regulated, not only optimizing the adsorption behavior of reaction intermediates but also accelerating the kinetics of hydrogen evolution reaction. The synthesized Ru/C60‐300 exhibits remarkable performance for hydrogen evolution in an alkaline condition. This study demonstrates a facile and efficient method for synthesizing effective fullerene‐supported metal cluster catalysts without any pretreatment and additional reducing agent.

Wet-chemical synthesis of Co3Mo3C-based electrocatalysts for oxygen reduction and evolution reactions

Abstract In recent years, efforts have been made to adapt secondary metal–air batteries for practical rechargeable applications through the development of bifunctional catalysts, which are highly active in both oxygen reduction reaction and oxygen evolution reaction. Molybdenum carbides, known for their high chemical durability and electrical conductivity, are being investigated as electrode materials for hydrogen evolution reactions in water electrolysis. In this study, we found a new wet chemical synthesis of cobalt-molybdenum-based carbides. Especially, the synthesized Mn-doped Co₃(Mo₀.₉Mn₀.₁)₃C catalyst gave a remarkable activity for both oxygen evolution reaction and oxygen reduction reaction, showing significant potential for the advancement of metal–air batteries as secondary batteries.

A Supramolecular-Nanocage-Based Framework Stabilized by π-π Stacking Interactions with Enhanced Photocatalysis.

π frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π-π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular-nanocage-based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π-π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π-2). π-2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π-2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co-catalyst, the hydrogen evolution rate reaches a record-high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π-2 to the highly active Pt upon illumination. π-2 represents the unique stable supramolecular-cage-based π framework with excellent photocatalytic activity.

Bi-metallic electrochemical deposition on 3D pyrolytic carbon architectures for potential application in hydrogen evolution reaction

ABSTRACT 3D printing has emerged as a highly efficient process for fabricating electrodes in hydrogen evolution through water splitting, whereas metals are the most popular choice of materials in hydrogen evolution reactions (HER) due to their catalytic activity. However, current 3D printing solutions face challenges, including high cost, low surface area, and sub-optimal performance. In this work, we introduce metal-deposited 3D printed pyrolytic carbon (PyC) as a facile and cost-effective HER electrode. We adopt an integrated approach of resin 3D printing, pyrolysis, and electrochemical metal deposition. 3D printing of a resin and its subsequent pyrolysis led to 3D complex architectures of the conductive substrate, facilitating the electrochemical metal deposition and leading to layered 3D metal architecture. Both monolayers of metals (such as copper and nickel) and bi-metallic 3D PyC structures are demonstrated. Each metal layer thickness ranges from 6 to10 µm. The metal coatings, particularly the bi-metallic configurations, result in achieving significantly higher mechanical properties under compressive loading and improved electrical properties due to the synergistic contributions from each metal counterpart. The metalized PyC structures are further demonstrated for HER catalysts, contributing to the development of highly efficient and durable catalyst systems for hydrogen production. Among the materials studied here, Ni@Cu bimetallic 3D PyC electrodes are particularly well-suited, demonstrating a low HER overpotential value of 264 mV (100 mA/cm2, KOH (1 M)) with corresponding Tafel slopes of 107 mV/dec, with exceptional stability during a 10 h operation at a high applied current of −50 mA/cm2.

Carbon nanomaterials for efficient oxygen and hydrogen evolution reactions in water splitting: A review

Water splitting has gained significant attention as a means to produce clean and sustainable hydrogen fuel through the electrochemical or photoelectrochemical decomposition of water. Efficient and cost-effective water splitting requires the development of highly active and stable catalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Carbon nanomaterials, including carbon nanotubes, graphene, and carbon nanofibers, etc., have emerged as promising candidates for catalyzing these reactions due to their unique properties, such as high surface area, excellent electrical conductivity, and chemical stability. This review article provides an overview of recent advancements in the utilization of carbon nanomaterials as catalysts or catalyst supports for the OER and HER in water splitting. It discusses various strategies employed to enhance the catalytic activity and stability of carbon nanomaterials, such as surface functionalization, hybridization with other active materials, and optimization of nanostructure and morphology. The influence of carbon nanomaterial properties, such as defect density, doping, and surface chemistry, on electrochemical performance is also explored. Furthermore, the article highlights the challenges and opportunities in the field, including scalability, long-term stability, and integration of carbon nanomaterials into practical water splitting devices. Overall, carbon nanomaterials show great potential for advancing the field of water splitting and enabling the realization of efficient and sustainable hydrogen production.

Corrolato(oxo)antimony(V) Dimer with Hydrogen-Bond Donor Groups in Secondary Coordination Sphere as a Catalyst for Hydrogen Evolution Reaction.

The focus is on developing alternative molecular catalysts using main-group elements and implementing strategic improvements for sustainable hydrogen production. For this purpose, a FB corrole with a (2-(2-((4-methylphenyl)sulfonamido)ethoxy)phenyl) group inserted into the meso position (C-10) of the corrole, along with its high-valent (corrolato)(oxo)antimony(V) dimer, was synthesized. In the crystal structure analysis of the FB corrole and the (corrolato)(oxo)antimony(V) dimer complex, it was noted that the sulfonamido group in the ligand periphery sits atop the corrole ring. The electrochemical hydrogen evolution reaction (HER) of the (corrolato)(oxo)antimony(V) dimer was studied and compared with a previously reported (corrolato)(oxo)antimony(V) complex, which lacks hydrogen-bond donor groups in the secondary coordination sphere. The newly designed molecules, featuring hydrogen-bond donor groups in the secondary coordination sphere, demonstrated clear superiority in the electrochemical HER. Controlled potential electrolysis was employed to evaluate the charge accumulation associated with hydrogen generation in a homogeneous three-electrode system in the presence of 50 mM TFA. The produced hydrogen exhibits a Faradaic efficiency of approximately 80.96%, a turnover frequency (TOF) of 0.44 h-1, and a production rate of 52.83 μL h-1, highlighting the effective catalytic activity of the (corrolato)(oxo)antimony(V) dimer in hydrogen evolution.

Electrodeposited NiB Films as Bifunctional Electrocatalysts in Alkaline Water Electrolizer

Abstract Sustainable electrochemical energy generation requires cost-effective, noble-metal-free electrocatalysts for hydrogen and oxygen production in electrolyzers. This study used electrodeposition to create crystalline NiB films with different boron (B) contents—Ni-B(1.17 wt.%), Ni-B(1.06 wt.%), Ni-B(0.94 wt.%), and Ni-B(0.89 wt.%)—on FTO substrates. These films were tested as bifunctional electrocatalyst electrodes for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline media. The NiB films' composition and morphology were analyzed using SEM, AFM, XRD, GD-OES, and XPS. Linear sweep voltammetry assessed their electrocatalytic performance. Higher B content in the films promoted the formation of electroactive NiOOH, enhancing the OER. The Ni-B(1.17 wt.%) electrode required an overpotential of 380 mV to reach 10 mA cm⁻² for OER, while the Ni-B(1.06 wt.%) electrode required 146 mV for the same current density for HER. An alkaline water electrolyzer using Ni-B(1.17 wt.%) as the anode and Ni-B(1.06 wt.%) as the cathode achieved a current density of 10 mA cm⁻² at 1.71 V for overall water splitting. The system showed stability over 12 hours of testing. The results indicate that NiB films on FTO substrates are promising, low-cost bifunctional electrocatalysts for alkaline water electrolysis, offering an alternative to noble-metal-based electrocatalysts.

Electronic Structure Engineering of Single-Atom Tungsten on Vacancy-enriched V3S4 Nanosheets for Efficient Hydrogen Evolution.

Constructing single-atom catalysts (SACs) and optimizing the electronic structure between metal atoms and support interactions is deemed one of the most effective strategies for boosting the catalytic kinetics of the hydrogen evolution reaction (HER). Herein, a sulfur vacancy defect trapping strategy is developed to anchor tungsten single atoms onto ultrathin V3S4 nanosheets with a high loading of 25.1wt.%. The obtained W-V3S4 catalyst exhibits a low overpotential of 54mV at 10mA cm-2 and excellent long-term stability in alkaline electrolytes. Density functional theory calculations reveal that the in situ anchoring of W single atoms triggers the delocalization and redistribution of electron density, which effectively accelerates water dissociation and facilitates hydrogen adsorption/desorption, thus enhancing HER activity. This work provides valuable insights into understanding highly active single-atom catalysts for large-scale hydrogen production.

Powering Hydrogen Evolution Reaction by Precise Control Over A Cu‐Ni Bimetallic Electrocatalyst

ABSTRACTPrecious metals are effective catalysts for the hydrogen evolution reaction, but their high cost with complicated operation steps drives people to search for non–noble‐metal alternatives. Building rational design concept for efficient electrocatalyst relies on the capability to control the structure and composition. Herein, a Ni/Cu bimetallic mesoporous MOFs with 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid as the robust ligand has been assembled via a one‐step solvothermal method. Due to the extensive conjugate plane and high nitrogen content, the catalyst possesses large pore size of 17 nm and fast electron transfer rate, which favors hydrogen bubble overflow and exposes more active sites to solid–liquid interfaces. The bimetallic interaction between highly conductive Cu ions and Ni ions allows it to improve charge migration and realize excellent conductivity. The functionalized electrode requires an overpotential of 132 mV to achieve 10 mA current density with a small Tafel slope (87.7 mV·dec−1) and continuous electrolysis for 24 h.

Bifunctional SnO2/NiO/rGO nanocomposite electrode for hydrogen evolution reaction and detection of winter wheat cold-resistant RNA.

Aconvenient, non-toxic, and low-cost tin dioxide (SnO2)/nickel oxide (NiO)/reduced graphene oxide (rGO) nanocatalytic electrode was investigated, which can effectively promote the hydrogen evolution reaction and can also be used to construct a sensitive winter wheat cold-tolerant RNA sensor. Due to the good synergy and photocurrent generation between SnO2 and NiO, which accelerates the electron transfer and catalyzes the hydrolysis reaction, the resultant data for the hydrogen evolution reaction in alkaline environment of this material are very impressive, with cathodic current densities of up to 10mAcm-2. The marvelous heterostructures and photovoltaic properties form a signal amplification system, which enables the nanocomposites to have an excellent linear sensitivity in low-concentration RNA solutions. The single-stranded complementary RNA of the target RNA was immobilized on the surface of the nanocomposites, which enabled the materials to recognize the target RNA under enzyme-free conditions. The test results showed that the modified electrode materials had good single detection performance in a wide linear range from 0.1nM to 2mM, with the limit of detection (LOD) of 0.078nM. The developed nanocomposite electrode has good performance in hydrogen evolution and winter wheat cold-resistant RNA detection, and is a bifunctional device with superior performance.

Microwave‐assisted control of PtNi nanoalloy clusters on the nitrogen‐doped graphene oxide for energy conversion with oxygen reduction reaction and hydrogen evolution reaction

AbstractResearch on the production and utilization of hydrogen energy is essential to overcome the environmental issues caused by fossil fuels. Herein, we anchor PtNi nanoalloy clusters (Pt‐Ni NACs) on nitrogen‐doped graphene oxide (NrGO) by a facile microwave‐assisted synthesis and analyze the variations of catalyst properties based on the PtNi composition and the presence of nitrogen. Ni inclusion in the Pt matrix can induce lattice strain and change the electronic structure, while the doped nitrogen into the graphene can enhance electron transfer and improve the durability of the catalyst through strong chemical bonding with the alloy clusters. TEM analysis discovers that the NACs are uniformly decorated in a few‐nanometer‐size on the graphene surface, and the formation of the PtNi NACs and structural changes according to composition are confirmed through XRD and XPS. In addition, the structural changes due to N‐doping and its bonding with the NACs are observed through Raman spectroscopy and XPS. Electrochemical measurements reveal that Pt2.6Ni NACs/NrGO exhibits the highest ORR onset potential (0.893 V) and the lowest HER overpotential at 10 mA cm−2 (22 mV) among other catalysts, and those activities are almost unchanged under long‐term durability tests. From these results, Pt2.6Ni NACs/NrGO is utilized in a zinc‐air battery (ZAB) system, demonstrating better battery performance than commercial Pt and Ir‐based catalysts. Moreover, it is applied to hydrogen collection, showing linear trend in hydrogen production over time, confirming the catalyst's availability in hydrogen production and utilization.image

Quasi Solid Polyzwitterion- Polyacrylamide Electrolytes for Rechargeable Zinc-Ion Battery

Zinc-ion batteries have attracted significant attention due to their low cost, rechargeability, and superior safety features. In fact, the use of aqueous electrolytes negatively affects battery performance due to the solid electrolyte interface (SEI), creating zinc corrosion, hydrogen evolution reaction (HER), and dendrite formation. To address these challenges, quasi-solid electrolytes (QSE) based on polyacrylamide-poly (3-(1-vinyl-3-imidazolio) propanesulfonate) (PAM/PVIPS) have been developed. PAM stands out as matrix QSE due to its excellent flexibility and electrochemical stability. PVIPS offers a well-defined pathway for ion transportation caused by cationic and anionic groups in structure. Clearly, the asymmetrical zinc cell with PAM/PVIPS QSE effectively reduces the overpotential profile, prolongs the stabilized zinc plating/stripping and enhances ionic conductivity, compared to PAM QSE. Additionality, the performance of Zn||δ-MnO2 is also enhanced with PAM/PVIPS QSE, yielding the specific capacity value of 65 mAh g-1, which is superior to the pristine PAM QSE (56 mAh g-1).

Stable Zinc Metal Battery Development: Using Fibrous Zirconia for Rapid Surface Conduction of Zinc Ions With Modified Water Solvation Structure.

The two most critical technical issues in Zn-based batteries, dendrite formation, and hydrogen evolution reaction, can be simultaneously addressed by introducing negatively charged fibrous ZrO2 as a separator. Electron redistribution between ZrO2 and Zn2+ ions renders the ZrO2 surface a preferred adsorption site for Zn2+ ions, making surface conduction the primary ion-transport mode. Surface conduction enables fibrous ZrO2 to exhibit a 6.54 times higher single-Zn-ion conductivity than that of conventional glass fiber, minimizing the concentration gradient of Zn2+ and suppressing dendrite formation. Additionally, strong Zr─O─Zn bonding stabilizes the Zn2+ ions with fewer solvated H2O molecules (≈2), preventing water molecules from approaching the electrode surface, as evidenced by a 58.8% decrease in the hydrogen evolution rate. Consequently, the cycling stability of a fibrous-ZrO2-based Zn/Zn symmetric cell (3000h at 1mAhcm-2 and 5mAcm-2) is approximately ten times greater than that of the conventional variant. Furthermore, a fibrous-ZrO2-based Zn-I2 full cell exhibits a notably high energy density (271.4Whkg-1) as well as a long lifespan (≈5000 cycles) at an ultrahigh current density (4Ag-1).

The electrochemical synthesis of urea on triatomic cluster/Cu catalysts: A theoretical study

Urea (NH2CONH2), a crucial nitrogen fertilizer and industrial raw material, is typically synthesized under rigorous reaction conditions. Currently, the electrocatalytic transformation of N2 and CO2 into urea is a promising strategy. However, finding a high-selectivity and high-activity catalyst remains a significant challenge. Herein, the activity of a series of transition metal clusters (VIII and IB groups) on copper-based catalysts for electrochemical coupling of CO2 and N2 has been systematically studied to produce urea via density functional theory (DFT). Most catalysts exhibit good thermodynamic stability and accomplish co-adsorb CO2 and N2. Notably, Fe3 and Ni3/Cu100 catalysts achieve C-N coupling via *CO and *N2, whereas Ru3, Rh3, Os3, and Ir3/Cu100 catalysts accomplish C-N coupling via *CO and *NHNH. Among all catalysts, the Ni3/Cu100 catalyst features excellent catalytic activity with a rate-determining step as low as 0.480 eV, and its C-N coupling only needs to overcome a barrier of 0.844 eV. Additionally, the Ni3/Cu100 catalyst can effectively inhibit the hydrogen evolution reaction (HER), further protonation of *CO and ammonia formation, thereby ensuring high selectivity for urea. Electronic structures analysis further reveals an “acceptance-donation” mechanism for the activation of *CO2 and *N2, with the introduction of the Ni3 cluster showing a decisive role. Therefore, this study may establish the foundation for the electrochemical synthesis of urea.