Threshold current density for diffusion-controlled stability of electrolytic surface nanobubbles.

Understanding the stability mechanism of surface micro/nanobubbles adhered to gas-evolving electrodes is essential for improving the efficiency of water electrolysis, which is known to be hindered by the bubble coverage on electrodes. Using molecular simulations, the diffusion-controlled evolution of single electrolytic nanobubbles on wettability-patterned nanoelectrodes is investigated. These nanoelectrodes feature hydrophobic islands as preferential nucleation sites and allow the growth of nanobubbles in the pinning mode. In these simulations, a threshold current density distinguishing stable nanobubbles from unstable nanobubbles is found. When the current density remains below the threshold value, nucleated nanobubbles grow to their equilibrium states, maintaining their nanoscopic size. However, for the current density above the threshold value, nanobubbles undergo unlimited growth and can eventually detach due to buoyancy. Increasing the pinning length of nanobubbles increases the degree of nanobubble instability. By connecting the current density with the local gas oversaturation, an extension of the stability theory for surface nanobubbles [Lohse and Zhang, Phys. Rev. E 91, 031003(R) (2015)] accurately predicts the nanobubble behavior found in molecular simulations, including equilibrium contact angles and the threshold current density. For larger systems that are not accessible to molecular simulations, continuum numerical simulations with the finite difference method combined with the immersed boundary method are performed, again demonstrating good agreement between numerics and theories.

Nuclear spin effects in biological processes.

Traditionally, nuclear spin is not considered to affect biological processes. Recently, this has changed as isotopic fractionation that deviates from classical mass dependence was reported both in vitro and in vivo. In these cases, the isotopic effect correlates with the nuclear magnetic spin. Here, we show nuclear spin effects using stable oxygen isotopes (16O, 17O, and 18O) in two separate setups: an artificial dioxygen production system and biological aquaporin channels in cells. We observe that oxygen dynamics in chiral environments (in particular its transport) depend on nuclear spin, suggesting future applications for controlled isotope separation to be used, for instance, in NMR. To demonstrate the mechanism behind our findings, we formulate theoretical models based on a nuclear-spin-enhanced switch between electronic spin states. Accounting for the role of nuclear spin in biology can provide insights into the role of quantum effects in living systems and help inspire the development of future biotechnology solutions.

Anode electrolysis of sulfides.

Traditional sulfide metallurgy produces harmful sulfur dioxide and is energy intensive. To this end, we develop an anode electrolysis approach in molten salt by which sulfide is electrochemically split into sulfur gas at a graphite inert anode while releasing metal ions that diffuse toward and are deposited at the cathode. The anodic splitting dictates the "sulfide-to-metal ion and sulfur gas" conversion that makes the reaction recur continuously. Using this approach, Cu2S is converted to sulfur gas and Cu in molten LiCl-KCl at 500 °C with a current efficiency of 99% and energy consumption of 0.420 kWh/kg-Cu (only considering the electricity for electrolysis). Besides Cu2S, the anode electrolysis can extract Cu from Cu matte that is an intermediate product from the traditional sulfide smelting process. More broadly, Fe, Ni, Pb, and Sb are extracted from FeS, CuFeS2, NiS, PbS, and Sb2S3, providing a general electrochemical method for sulfide metallurgy.

High-performance seawater oxidation by a homogeneous multimetallic layered double hydroxide electrocatalyst.

SignificanceSeawater is one of the most abundant resources on Earth. Direct electrolysis of seawater is a transformative technology for sustainable hydrogen production without causing freshwater scarcity. However, this technology is severely impeded by a lack of robust and active oxygen evolution reaction (OER) electrocatalysts. Here, we report a highly efficient OER electrocatalyst composed of multimetallic layered double hydroxides, which affords superior catalytic performance and long-term durability for high-performance seawater electrolysis. To the best of our knowledge, this catalyst is among the most active for OER and it advances the development of seawater electrolysis technology.

Controlled growth of a high selectivity interface for seawater electrolysis.

Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhOx-graphdiyne (GDY/RhOx/GDY) were constructed by in situ-controlled growth of GDY on RhOx nanocrystals. A double layer interface of sp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites of sp-C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawing sp-C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm-2 at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derived sp-C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.

Solidophobic Surface for Electrochemical Extraction of High-Valued Mg(OH)2 Coupled with H2 Production from Seawater.

A significant challenge in direct seawater electrolysis is the rapid deactivation of the cathode due to the large scaling of Mg(OH)2. Herein, we synthesized a Pt-coated highly disordered NiCu alloy (Pt-NiCu alloy) electrode with superior solidophobic behavior, enabling stable hydrogen generation (100 mA cm-2, >1000 h durability) and simultaneous production of Mg(OH)2 (>99.0% purity) in electrolyte enriched with Mg2+ and Ca2+. The unconventional solidophobic property primarily stems from the high surface energy of the NiCu alloy substrate, which facilitates the adsorption of surface water and thereby compels the bulk formation of Mg(OH)2 via homogeneous nucleation. The discovery of this solidophobic electrode will revolutionarily simplify the existing techniques for seawater electrolysis and increase the economic viability for seawater electrolysis.

Engineering the Co(II)/Co(III) Redox Cycle and Coδ+ Species Shuttle for Nitrate-to-Ammonia Conversion.

Electroreduction of waste nitrate to valuable ammonia offers a green solution for environmental restoration and energy storage. However, the electrochemical self-reconstruction of catalysts remains a huge challenge in terms of maintaining their stability, achieving the desired active sites, and managing metal leaching. Herein, we present an electrical pulse-driven Co surface reconstruction-coupled Coδ+ shuttle strategy for the precise in situ regulation of the Co(II)/Co(III) redox cycle on the Co-based working electrode and guiding the dissolution and redeposition of Co-based particles on the counter electrode. As result, the ammonia synthesis performance and stability are significantly promoted while cathodic hydrogen evolution and anodic ammonia oxidation in a membrane-free configuration are effectively blocked. A high rate of ammonia production of 1.4 ± 0.03 mmol cm-2 h-1 is achieved at -0.8 V in a pulsed system, and the corresponding nitrate-to-ammonia Faraday efficiency is 91.7 ± 1.0%. This work holds promise for the regulation of catalyst reactivity and selectivity by engineering in situ controllable structural and chemical transformations.

Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.

Perovskites are an important class of oxygen evolution reaction (OER) catalysts due to highly tunable compositions and adaptable characteristics. However, perovskite-based catalysts can have limited atom utilization efficiency due to large particle size, resulting in low mass activity. Herein, Cobalt nanoparticles are exsolved from La0.2+2x Ca0.7-2x Ti1-x Cox O3 perovskite and applied in OER. Upon reduction in the 5% H2 /N2 atmosphere at 800 °C for 2 h, the Co exsolved perovskite catalyst (R-LCTCo0.11) exhibits optimal OER performance. The mass activity of R-LCTCo0.11 reaches ≈1700 mA mg-1 at an overpotential of 450 mV, which is 17 times and 3 times higher than that of LCTCo0.11 (97 mA mg-1 ) and R-Mix (560 mA mg-1 ) catalysts respectively, surpassing the benchmark catalyst RuO2 (42.7 mA mg-1 of oxide at η = 470 mV). Electrochemical impedance spectroscopy (EIS) data reveals that R-LCTCo0.11 has the lowest charge transfer resistance (Rct  = 58 Ω), demonstrating the highest catalytic and kinetic activity for OER. Furthermore, this catalyst shows high stability during an accelerated durability test of 10 h electrolysis and 1000 cycles cyclic voltammetry (CV). This work demonstrates that nanoparticle exsolution from a doped perovskite is an effective strategy for improving the atom utilization efficiency in OER.

Tungstate Intercalated NiFe Layered Double Hydroxide Enables Long-Term Alkaline Seawater Oxidation.

Renewable electricity-driven seawater splitting presents a green, effective, and promising strategy for building hydrogen (H2)-based energy systems (e.g., storing wind power as H2), especially in many coastal cities. The abundance of Cl- in seawater, however, will cause severe corrosion of anode catalyst during the seawater electrolysis, and thus affect the long-term stability of the catalyst. Herein, seawater oxidation performances of NiFe layered double hydroxides (LDH), a classic oxygen (O2) evolution material, can be boosted by employing tungstate (WO4 2-) as the intercalated guest. Notably, insertion of WO4 2- to LDH layers upgrades the reaction kinetics and selectivity, attaining higher current densities with ≈100% O2 generation efficiency in alkaline seawater. Moreover, after a 350 h test at 1000 mA cm-2, only trace active chlorine can be detected in the electrolyte. Additionally, O2 evolution follows lattice oxygen mechanism on NiFe LDH with intercalated WO4 2-.

Increased Readiness for Water Splitting: NiO-Induced Weakening of Bonds in Water Molecules as Possible Cause of Ultra-Low Oxygen Evolution Potential.

The development of non-precious metal-based electrodes that actively and stably support the oxygen evolution reaction (OER) in water electrolysis systems remains a challenge, especially at low pH levels. The recently published study has conclusively shown that the addition of haematite to H2SO4 is a highly effective method of significantly reducing oxygen evolution overpotential and extending anode life. The far superior result is achieved by concentrating oxygen evolution centres on the oxide particles rather than on the electrode. However, unsatisfactory Faradaic efficiencies of the OER and hydrogen evolution reaction (HER) parts as well as the required high haematite load impede applicability and upscaling of this process. Here it is shown that the same performance is achieved with three times less metal oxide powder if NiO/H2SO4 suspensions are used along with stainless steel anodes. The reason for the enormous improvement in OER performance by adding NiO to the electrolyte is the weakening of the intramolecular O─H bond in the water molecules, which is under the direct influence of the nickel oxide suspended in the electrolyte. The manipulation of bonds in water molecules to increase the tendency of the water to split is a ground-breaking development, as shown in this first example.

FeNi2 S4 -A Potent Bifunctional Efficient Electrocatalyst for the Overall Electrochemical Water Splitting in Alkaline Electrolyte.

For a carbon-neutral society, the production of hydrogen as a clean fuel through water electrolysis is currently of great interest. Since water electrolysis is a laborious energetic reaction, it requires high energy to maintain efficient and sustainable production of hydrogen. Catalytic electrodes can reduce the required energy and minimize production costs. In this context, herein, a bifunctional electrocatalyst made from iron nickel sulfide (FeNi2 S4 [FNS]) for the overall electrochemical water splitting is introduced. Compared to Fe2 NiO4 (FNO), FNS shows a significantly improved performance toward both OER and HER in alkaline electrolytes. At the same time, the FNS electrode exhibits high activity toward the overall electrochemical water splitting, achieving a current density of 10 mA cm-2 at 1.63 V, which is favourable compared to previously published nonprecious electrocatalysts for overall water splitting. The long-term chronopotentiometry test reveals an activation followed by a subsequent stable overall cell potential at around 2.12 V for 20 h at 100 mA cm-2 .

Stability of Ni-Fe-Layered Double Hydroxide Under Long-Term Operation in AEM Water Electrolysis.

Anion exchange membrane water electrolysis (AEMWE) is an attractive method for green hydrogen production. It allows the use of non-platinum group metal catalysts and can achieve performance comparable to proton exchange membrane water electrolyzers due to recent technological advances. While current systems already show high performances with available materials, research gaps remain in understanding electrode durability and degradation behavior. In this study, the performance and degradation tracking of a Ni3Fe-LDH-based single-cell is implemented and investigated through the correlation of electrochemical data using chemical and physical characterization methods. A performance stability of 1000 h, with a degradation rate of 84 µV h-1 at 1 A cm-2 is achieved, presenting the Ni3Fe-LDH-based cell as a stable and cost-attractive AEMWE system. The results show that the conductivity of the formed Ni-Fe-phase is one key to obtaining high electrolyzer performance and that, despite Fe leaching, change in anion-conducting binder compound, and morphological changes inside the catalyst bulk, the Ni3Fe-LDH-based single-cells demonstrate high performance and durability. The work reveals the importance of longer stability tests and presents a holistic approach of electrochemical tracking and post-mortem analysis that offers a guideline for investigating electrode degradation behavior over extended measurement periods.

Designing Efficient Non-Precious Metal Electrocatalysts for High-Performance Hydrogen Production: A Comprehensive Evaluation Strategy.

Developing abundant Earth-element and high-efficient electrocatalysts for hydrogen production is crucial in effectively reducing the cost of green hydrogen production. Herein, a strategy by comprehensively considering the computational chemical indicators for H* adsorption/desorption and dehydrogenation kinetics to evaluate the hydrogen evolution performance of electrocatalysts is proposed. Guided by the proposed strategy, a series of catalysts are constructed through a dual transition metal doping strategy. Density Functional Theory (DFT) calculations and experimental chemistry demonstrate that cobalt-vanadium co-doped Ni3N is an exceptionally ideal catalyst for hydrogen production from electrolyzed alkaline water. Specifically, Co,V-Ni3N requires only 10 and 41 mV in alkaline electrolytes and alkaline seawater, respectively, to achieve a hydrogen evolution current density of 10 mA cm-2. Moreover, it can operate steadily at a large industrial current density of 500 mA cm-2 for extended periods. Importantly, this evaluation strategy is extended to single-metal-doped Ni3N and found that it still exhibits significant universality. This study not only presents an efficient non-precious metal-based electrocatalyst for water/seawater electrolysis but also provides a significant strategy for the design of high-performance catalysts of electrolyzed water.

Boosting Alkaline Seawater Oxidation of CoFe-layered Double Hydroxide Nanosheet Array by Cr Doping.

The pursuit of stable and efficient electrocatalysts toward seawater oxidation is of great interest, yet it poses considerable challenges. Herein, the utilization of Cr-doped CoFe-layered double hydroxide nanosheet array is reported on nickel-foam (Cr-CoFe-LDH/NF) as an efficient electrocatalyst for oxygen evolution reaction in alkaline seawater. The Cr-CoFe-LDH/NF catalyst can achieve current densities of 500 and 1000 mA cm -2 with remarkably low overpotentials of only 334 and 369 mV, respectively. Furthermore, it maintains at least 100 h stability when operated at 500 mA cm-2.

Dual-Functional Ru/Ni-B-P Electrocatalyst Toward Accelerated Water Electrolysis and High-Stability.

Development of advanced electrocatalysts for the green hydrogen production by water electrolysis is an important task to reduce the climate and environmental issues as well as to meet the future energy demands. Herein, Ru/Ni-B-P sphere electrocatalyst is demonstrated by a combination of hydrothermal and soaking approaches, meeting the industrial requirement of low cell voltage with stable high-current operation. The Ru/Ni-B-P sphere catalyst demonstrates low overpotentials of 191 and 350 mV at 300 mA cm-2 with stable high current operation, ranking it as one of the best oxygen evolution reaction (OER) electrocatalysts. The bifunctional 2-E system demonstrates a low cell voltage of 2.49 V at 2000 mA cm-2 in 6 m KOH at 60 °C of harsh industrial operation condition. It also demonstrates outstanding stability with continuous 120 h (5 days) CA operation at 1000 mA cm-2. Further, the hybrid configuration of Ru/Ni-B-P || Pt/C being paired with the conventional benchmark electrode demonstrates a record low 2-E cell voltage of 2.40 V at 2000 mA cm-2 in 6 m KOH and excellent stability at high current of 1500 mA cm-2 under industrial operational condition.

Strain and Shell Thickness Engineering in Pd3 Pb@Pt Bifunctional Electrocatalyst for Ethanol Upgrading Coupled with Hydrogen Production.

The ethanol oxidation reaction (EOR) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts for both EOR and hydrogen evolution reaction (HER) is a major challenge. Herein, the synthesis of Pd3 Pb@Pt core-shell nanocubes with controlled shell thickness by Pt-seeded epitaxial growth on intermetallic Pd3 Pb cores is reported. The lattice mismatch between the Pd3 Pb core and the Pt shell leads to the expansion of the Pt lattice. The synergistic effects between the tensile strain and the core-shell structures result in excellent electrocatalytic performance of Pd3 Pb@Pt catalysts for both EOR and HER. In particular, Pd3 Pb@Pt with three Pt atomic layers shows a mass activity of 8.60 A mg-1 Pd+Pt for ethanol upgrading to acetic acid and close to 100% of Faradic efficiency for HER. An EOR/HER electrolysis system is assembled using Pd3 Pb@Pt for both the anode and cathode, and it is shown that low cell voltage of 0.75 V is required to reach a current density of 10 mA cm-2 . The present work offers a promising strategy for the development of bifunctional catalysts for hybrid electrocatalytic reactions and beyond.

Pulsed Electrolysis Promotes CO2 Reduction to Ethanol on Heterostructured Cu2O/Ag Catalysts.

The electrochemical conversion of carbon dioxide (CO2) into ethanol with high added value has attracted increasing attention. Here, an efficient catalyst with abundant Cu2O/Ag interfaces for ethanol production under pulsed CO2 electrolysis is reported, which is composed of Cu2O hollow nanospheres loaded with Ag nanoparticles (named as se-Cu2O/Ag). The CO2-to-ethanol Faradaic efficiency is prominently improved to 46.3% at a partial current density up to 417 mA cm-2 under pulsed electrolysis conditions in a neutral flow cell, notably outperforming conventional Cu catalysts during static electrolysis. In situ spectroscopy reveals the stabilized Cu+ species of se-Cu2O/Ag during pulsed electrolysis and the enhanced adsorbed CO intermediate (*CO)coverage on the heterostructured catalyst. Density functional theory (DFT) calculations further confirm that the Cu2O/Ag heterostructure stabilizes the *CO intermediate and promotes the coupling of *CO and adsorbed CH intermediate (*CH). Meanwhile, the stable Cu+ species under pulsed electrolysis favor the hydrogenation of adsorbed HCCOH intermediate (*HCCOH) to adsorbed HCCHOH intermediate (*HCCHOH) on the pathway to ethanol. The synergistic effect between the enhanced generation of *CO on Cu2O/Ag and regenerated Cu+ species under pulsed electrolysis steers the reaction pathway toward ethanol. This work provides some insights into selective ethanol production from CO2 electroreduction via combined catalyst design and non-steady state electrolysis.

Photo-Excited High-Spin State Ni (III) Species in Mo-Doped Ni3S2 for Efficient Urea Oxidation Reaction.

Designing robust catalysts for increasing the sluggish kinetics of the urea oxidation reaction (UOR) is challenging. Herein, the regulation of spin states for metal active sites by photoexcitation to facilitate the adsorption of urea and intermediates is demonstrated. Mo-doped nickel sulfide nanoribbon arrays (Mo-Ni3S2@NMF) with excellent light-trapping capacity are successfully prepared. Under AM 1.5G illumination, the activity of the Mo-Ni3S2@NMF exhibits a 50% improvement in the UOR current. Compared with those under dark conditions, Mo-Ni3S2@NMF achieve 10 mA cm-2 at 1.315 VRHE for UOR and 1.32 Vcell for urea electrolysis, which are decreases of 15 and 80 mV, respectively. The electron spin resonance, in situ Fourier transform infrared spectroscopy analysis and density functional theory calculations reveal that illumination led to the formation of Ni3+ active sites in a high-spin state, which strengthens the d-p orbital hybridization of Ni-N, hence facilitating the adsorption of urea. C─N cleavage of the *CONN intermediate is further inhibited, which promotes the oxidation of urea molecules via the active N2 pathway, thereby accelerating the UOR rate.

Deciphering the In Situ Reconstruction of Metal Phosphide/Nitride Dual Heterostructures for Robust Alkaline Hydrogen Evolution Above 3 A cm-2.

Hydrogen evolution reaction (HER) in neutral or alkaline electrolytes is appealing for sustainable hydrogen production driven by water splitting, but generally suffers from unsatisfied catalytic activities at high current densities owing to extra kinetic energy barriers required to generate protons through water dissociation. In response, here, a competitive Ni3N/Co3N/CoP electrocatalyst with multifunctional interfacial sites and multilevel interfaces, in which Ni3N/CoP performs as active sites to boost initial water dissociation and Co3N/CoP accelerates subsequent hydrogen adsorption process as confirmed by density functional theory calculations and in situ X-ray photoelectron spectroscopy analysis, is reported. This hybrid catalyst possesses extraordinary HER activity in base, featured by extremely low overpotentials of 115 and 142 mV to afford 500 and 1000 mA cm-2, respectively, outperforming most ever-reported metal phosphides-based catalysts. This catalyst presents an ultrahigh current density of 3545 mA cm-2 by a factor of 4.96 relative to noble Pt/C catalysts (715 mA cm-2) at 0.2 V. Assembled with Fe(PO3)2/Ni2P anode, industrial-level current densities of 500/1000 mA cm-2 at ultralow cell voltages of 1.62/1.66 V for overall water electrolysis with outstanding long-term stability are actualized. More interestingly, this hybrid catalyst also performs well in acidic, neutral freshwater, and seawater requiring relatively low overpotentials of 140, 290, and 331 mV to reach 500 mA cm-2. Particularly, this catalyst can withstand electrochemical corrosion without obvious activity decay at the industrial-level current densities for over 100 h in base. This work provides a cornerstone for the construction of advanced catalysts operated in different pH environments.

Phase Electronic Structure Tuning via Pt, P-Doped Ni4Mo-Implanted Ti4O7 for Highly Efficient Water Splitting and Mg/Seawater Batteries.

Fine-tuning nanoscale structures, morphologies, and electronic states are crucial for creating efficient water-splitting electrocatalysts. In this study, a method for electronic structure engineering to enhance overall water splitting in a corrosion-resistant electrocatalyst matrix by integrating Pt, P dual-doped Ni4Mo electrocatalysts onto a Ti4O7 nanorod grown on carbon cloth (Pt, P-Ni4Mo-Ti4O7/CC) is introduced. By optimizing platinum and phosphorus concentrations to 1.18% and 2.42%, respectively, low overpotentials are achieved remarkably: 24 mV at 10 mA cm-2 for the hydrogen evolution reaction and 290 mV at 20 mA cm-2 for the oxygen evolution reaction in 1.0 m KOH. These values approach or surpass those of benchmark Pt-C and IrO2 catalysts. Additionally, the Pt, P-Ni4Mo-Ti4O7/CC bifunctional electrocatalyst displays low cell potentials across various mediums, maintaining excellent current retention (96% stability after 40 h in mimic seawater at 20 mA cm-2) and demonstrating strong corrosion resistance and suitability for seawater  electrolysis. As a cathode in magnesium/seawater batteries, it achieves a power density of 7.2 mW cm-2 and maintains stability for 100 h. Density functional theory simulations confirm that P, Pt doping-assisted electronic structure modifications augment electrical conductivity and active sites in the hybrid electrocatalysts.