Positively Charged Hollow Co Nanoshells by Kirkendall Effect Stabilized by Electron Sink for Alkaline Water Dissociation.

While cobalt (Co) exhibits a comparable energy barrier for H* adsorption/desorption to platinum in theory, it is generally not suitable for alkaline hydrogen evolution reaction (HER) because of unfavorable water dissociation. Here, the Kirkendall effect is adopted to fabricate positive-charged hollow metal Co (PHCo) nanoshells that are stabilized by MoO2 and chainmail carbon as the electron sink. Compared to the zero-valent Co, the PHCo accelerates the water dissociation and changes the rate-determining step from Volmer to Heyrovsky process. Alkaline HER occurs with a low overpotential of 59.0 mV at 10 mA cm-2. Operando Raman and first principles calculations reveal that the interfacial water to the PHCo sites and the accelerated proton transfer are conducive to the adsorption and dissociation of H2O molecules. Meanwhile, the upshifted d-band center of PHCo optimizes the adsorption/desorption of H*. This work provides a unique synthesis of hollow Co nanoshells via the Kirkendall effect and insights to water dissociation on catalyst surfaces with tailored charge states.

Pt-based graphene quantum dots for water dissociation.

It is widely recognized that Pt nanostructures exhibit favorable catalytic properties for several important technological reactions. Furthermore, selecting an appropriate support has the potential to enhance the catalytic activity of these materials. In this study, we investigate Pt nanoparticles deposited on quantum dots using quantum chemical calculations. We explore the utilization of low-dimensional carbonaceous support by employing graphene quantum dots (GQDs), which offer abundant active sites, such as edges, and diverse conformations. This provides excellent tuning possibilities for both chemical and physical properties. Our goal is to gather information on the alterations in electronic properties, charge redistribution and reactivity of platinum particles on GQD, also analyzing their potential role as catalysts in the water dissociation reaction. Based on thermodynamic and kinetic considerations, our calculations suggest that a Pt3nanoparticle adsorbed on the edge of the GQD exhibits favorable energetics, leading to a promising catalytic material.

Constructing a Built-In Electric Field To Accelerate Water Dissociation for Efficient Alkaline Hydrogen Evolution.

The alkaline hydrogen evolution reaction (HER) is intricately linked to the water dissociation kinetics. The quest for new strategies to accelerate this step is a pivotal aspect of enhancing the HER performance. Herein, we designed and synthesized a heterogeneous nickel phosphide/cobalt phosphide nanowire array grown on nickel foam (Ni2P/CoP/NF) to form a p-n junction structure. The built-in electric field (BEF) in the p-n junction optimizes the binding ability of hydrogen and hydroxyl intermediates, efficiently promoting water dissociation for the alkaline HER. Consequently, Ni2P/CoP/NF exhibits a lower overpotential of 58 and 118 mV at 30 and 100 mA cm-2, respectively, and high stability over 40 h at 300 mA cm-2 for the HER in 1 M KOH. Computational calculations combined with experiment results testify that the BEF presence in the p-n junction of Ni2P/CoP/NF effectively promotes water dissociation, regulates intermediate adsorption/desorption, and boosts electron transport. This study presents a rational design approach for high-performance heterogeneous electrocatalysts.

Manipulating heterointerface to boost formation and desorption of intermediates for highly efficient alkaline hydrogen evolution.

Promoting water dissociation and H intermediate desorption play a pivotal role in achieving highly efficient hydrogen evolution reaction (HER) in alkaline media but remain a great challenge. Herein, we rationally develop a unique W-doped NiSx/Ni heterointerface as a favorable HER electrocatalyst which was directly grown on the Cu nanowire foam substrate (W-NiSx/Ni@Cu) by the electrodeposition strategy. Benefiting from the rational design of the interfaces, the electronic coupling of the W-NiSx/Ni@Cu can be efficiently modulated to lower the HER kinetic barrier. The obtained W-NiSx/Ni@Cu exhibits an enhanced HER activity with a low overpotential of 38 mV at 10 mA cm-2 and a small Tafel value of 27.5 mV dec-1, and high stability during HER catalysis. In addition, in-situ Raman spectra reveal that the Ni2+ active sites preferentially adsorb OH intermediate. The theoretical calculation confirms that the water dissociation is accelerated by the construction of W-NiSx/Ni heterointerface and H intermediate desorption can be also promoted by H spillover from S active sites in W-NiSx to Ni active sites in metal Ni. This work offers a valuable reference for rational designing heterointerface of electrocatalysts and provides an available method to accelerate the HER kinetics for the ampere-level current density under low overpotential.

Enhanced Electrochemical CO2 Reduction to Formate over Phosphate-Modified In: Water Activation and Active Site Tuning.

Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

Boosting Efficient Alkaline Hydrogen Evolution Reaction of CoFe-Layered Double Hydroxides Nanosheets via Co-Coordination Mechanism of W-Doping and Oxygen Defect Engineering.

While surface defects and heteroatom doping exhibit promising potential in augmenting the electrocatalytic hydrogen evolution reaction (HER), their performance remains unable to rival that of the costly Pt-based catalysts. Yet, the concurrent modification of catalysts by integrating both approaches stands as a promising strategy to effectively address the aforementioned limitation. In this work, tungsten dopants are introduced into self-supported CoFe-layered double hydroxides (LDH) on nickel foam using a hydrothermal method, and oxygen vacancies (Ov) are further introduced through calcination. The analysis results demonstrated that tungsten doping reduces the Ov formation energy of CoFeW-LDH. The Ov acted as oxophilic sites, facilitating water adsorption and dissociation, and reducing the barrier for cleaving HO─H bonds from 0.64 to 0.14 eV. Additionally, Ov regulated the electronic structure of CoFeW-LDH to endow optimized hydrogen binding ability on tungsten atoms, thereby accelerating alkaline Volmer and Heyrovsky reaction kinetics. Specifically, the abundance of Ov induced a transition of tungsten from a six-coordinated to highly active four-coordinated structure, which becomes the active site for HER. Consequently, an ultra-low overpotential of 41 mV at 10 mA cm-2, and a low Tafel slope of 35 mV dec-1 are achieved. These findings offer crucial insights for the design of efficient HER electrocatalysts.

Cobalt Single-Atom Reverse Hydrogen Spillover for Efficient Electrochemical Water Dissociation and Dechlorination.

Efficient water dissociation to atomic hydrogen (H*) with restrained recombination of H* is crucial for improving the H* utilization for electrochemical dechlorination, but is currently limited by the lack of feasible electrodes. Herein, we developed a monolithic single-atom electrode with Co single atoms anchored on the inherent oxide layer of titanium foam (Co1-TiOx/Ti), which can efficiently dissociate water into H* and simultaneously inhibit the recombination of H*, by taking advantage of the single-atom reverse hydrogen spillover effect. Experimental and theoretical calculations demonstrated that H* could be rapidly generated on the oxide layer of titanium foam, and then overflowed to the adjacent Co single atom for the reductive dechlorination. Using chloramphenicol as a proof-of-concept verification, the resulting Co1-TiOx/Ti monolithic electrode exhibited an unprecedented performance with almost 100 % dechlorination at -1.0 V, far superior to that of traditional indirect reduction-driven commercial Pd/C (52 %) and direct reduction-driven Co1-N-C (44 %). Moreover, its dechlorination rate constant of 1.64 h-1 was 4.3 and 8.6 times more active than those of Pd/C (0.38 h-1) and Co1-N-C (0.19 h-1), respectively. Our research sheds light on the rational design of hydrogen spillover-related electrocatalysts to simultaneously improve the H* generation, transfer, and utilization for environmental and energy applications.

Highly Selective Acetylene-to-Ethylene Electroreduction Over Cd-Decorated Cu Catalyst with Efficiently Inhibited Carbon-Carbon Coupling.

Electrochemical acetylene reduction (EAR) employing Cu catalysts represents an environmentally friendly and cost-effective method for ethylene production and purification. However, Cu-based catalysts encounter product selectivity issues stemming from carbon-carbon coupling and other side reactions. We explored the use of secondary metals to modify Cu-based catalysts and identified Cd decoration as particular effective. Cd decoration demonstrated a high ethylene Faradaic efficiency (FE) of 98.38 % with well-inhibited carbon-carbon coupling reactions (0.06 % for butadiene FE at -0.5 V versus reversible hydrogen electrode) in a 5 vol % acetylene gas feed. Notably, ethylene selectivity of 99.99 % was achieved in the crude ethylene feed during prolonged stability tests. Theoretical calculations revealed that Cd metal accelerates the water dissociation on neighboring Cu surfaces allowing more H* to participate in the acetylene semi-hydrogenation, while increasing the energy barrier for carbon-carbon coupling, thereby contributing to a high ethylene semi-hydrogenation efficiency and significant inhibition of carbon-carbon coupling. This study provides a paradigm for a deeper understanding of secondary metals in regulating the product selectivity of EAR electrocatalysts.

Mnemonic Rutile-Rutile Interfaces Triggering Spontaneous Dissociation of Water.

Water interaction with mineral surfaces is a complex living system decisive for any photocatalytic process. Resolving the atomistic structure of mineral-water interfaces is thus crucial for understanding these processes. Fibrous rutile TiO2 , grown hydrothermally on twinned rutile seeds under acidic conditions, is studied in terms of interface translation, atomic structure, and surface chemistry in the presence of water, by means of advanced microscopy and spectroscopy methods combined with structure modeling and density functional theory calculations. It is shown that fibers while staying in stable separation during their growth, adopt a special crystallographic registry that is controlled by repulsion forces between fully hydroxylated and protonated (110) surfaces. During relaxation, a turbulent proton transfer and cracking of O─H bonds is observed, generating a strong acidic character via proton jump from bridge ─OHb to terminal ─OHt groups, and spontaneous dissociation of interfacial water via a transient protonation of the ─OHt groups. It is shown, that this specific interface structure can be implemented to induce acidic response in an initially neutral medium when re-immersed. This is thought to be the first demonstration of quantum-confined mineral-water interface, capable of memorizing its past and conveying its structurally encoded properties into a new environment.

Universal Platform for Robust Dual-Atom Doped 2D Catalysts with Superior Hydrogen Evolution in Wide pH Media.

Layered 2D transition metal dichalcogenides (TMDs) have been suggested as efficient substitutes for Pt-group metal electrocatalysts in the hydrogen evolution reaction (HER). However, poor catalytic activities in neutral and alkaline electrolytes considerably hinder their practical applications. Furthermore, the weak adhesion between TMDs and electrodes often impedes long-term durability and thus requires a binder. Here, a universal platform is reported for robust dual-atom doped 2D electrocatalysts with superior HER performance over a wide pH range media. V:Co-ReS2 on a wafer scale is directly grown on oxidized Ti foil by a liquid-phase precursor-assisted approach and subsequently used as highly efficient electrocatalysts. The catalytic performance surpasses that of Pt group metals in a high current regime (≥ 100 mA cm-2) at pH ≥ 7, with a high durability of more than 70 h in all media at 200 mA cm-2. First-principles calculations reveal that V:Co dual doping in ReS2 significantly reduces the water dissociation barrier and simultaneously enables the material to achieve the thermoneutral Gibbs free energy for hydrogen adsorption.

Comparison of H2O Adsorption and Dissociation Behaviors on Rutile (110) and Anatase (101) Surfaces Based on ReaxFF Molecular Dynamics Simulation.

The relationship between structure and reactivity plays a dominant role in water dissociation on the various TiO2 crystallines. To observe the adsorption and dissociation behavior of H2O, the reaction force field (ReaxFF) is used to investigate the dynamic behavior of H2O on rutile (110) and anatase (101) surfaces in an aqueous environment. Simulation results show that there is a direct proton transfer between the adsorbed H2O (H2Oad) and the bridging oxygen (Obr) on the rutile (110) surface. Compared with that on the rutile (110) surface, an indirect proton transfer occurs on the anatase (101) surface along the H-bond network from the second layer of water. This different mechanism of water dissociation is determined by the distance between the 5-fold coordinated Ti (Ti5c) and Obr of the rutile and anatase TiO2 surfaces, resulting in the direct or indirect proton transfer. Additionally, the hydrogen bond (H-bond) network plays a crucial role in the adsorption and dissociation of H2O on the TiO2 surface. To describe interfacial water structures between TiO2 and bulk water, the double-layer model is proposed. The first layer is the dissociated H2O on the rutile (110) and anatase (101) surfaces. The second layer forms an ordered water structure adsorbed to the surface Obr or terminal OH group through strong hydrogen bonding (H-bonding). Affected by the H-bond network, the H2O dissociation on the rutile (110) surface is inhibited but that on the anatase (101) surface is promoted.

Combined Electrospinning-Electrospraying for High-Performance Bipolar Membranes with Incorporated MCM-41 as Water Dissociation Catalysts.

Electrospinning has been demonstrated as a very promising method to create bipolar membranes (BPMs), especially as it allows three-dimensional (3D) junctions of entangled anion exchange and cation exchange nanofibers. These newly developed BPMs are relevant to demanding applications, including acid and base production, fuel cells, flow batteries, ammonia removal, concentration of carbon dioxide, and hydrogen generation. However, these applications require the introduction of catalysts into the BPM to allow accelerated water dissociation, and this remains a challenge. Here, we demonstrate a versatile strategy to produce very efficient BPMs through a combined electrospinning-electrospraying approach. Moreover, this work applies the newly investigated water dissociation catalyst of nanostructured silica MCM-41. Several BPMs were produced by electrospraying MCM-41 nanoparticles into the layers directly adjacent to the main BPM 3D junction. BPMs with various loadings of MCM-41 nanoparticles and BPMs with different catalyst positions relative to the junction were investigated. The membranes were carefully characterized for their structure and performance. Interestingly, the water dissociation performance of BPMs showed a clear optimal MCM-41 loading where the performance outpaced that of a commercial BPM, recording a transmembrane voltage of approximately 1.11 V at 1000 A/m2. Such an excellent performance is very relevant to fuel cell and flow battery applications, but our results also shed light on the exact function of the catalyst in this mode of operation. Overall, we demonstrate clearly that introducing a novel BPM architecture through a novel hybrid electrospinning-electrospraying method allows the uptake of promising new catalysts (i.e., MCM-41) and the production of very relevant BPMs.

Boosting the Proton-coupled Electron Transfer via Fe-P Atomic Pair for Enhanced Electrochemical CO2 Reduction.

Single-atom catalysts exhibit superior CO2 -to-CO catalytic activity, but poor kinetics of proton-coupled electron transfer (PCET) steps still limit the overall performance toward the industrial scale. Here, we constructed a Fe-P atom paired catalyst onto nitrogen doped graphitic layer (Fe1 /PNG) to accelerate PCET step. Fe1 /PNG delivers an industrial CO current of 1 A with FECO over 90 % at 2.5 V in a membrane-electrode assembly, overperforming the CO current of Fe1 /NG by more than 300 %. We also decrypted the synergistic effects of the P atom in the Fe-P atom pair using operando techniques and density functional theory, revealing that the P atom provides additional adsorption sites for accelerating water dissociation, boosting the hydrogenation of CO2 , and enhancing the activity of CO2 reduction. This atom-pair catalytic strategy can modulate multiple reactants and intermediates to break through the inherent limitations of single-atom catalysts.

Rh-dispersed Cu nanowire catalyst for boosting electrocatalytic hydrogenation of 5-hydroxymethylfurfural.

Electrocatalytic conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) presents a compelling strategy for the production of premium chemicals via the utilization of renewable energy sources. Exploring efficient catalytic systems to obtain highly selective BHMF has remained a giant challenge. A design strategy is proposed here to regulate active hydrogen (Hads) production in rhodium (Rh) nanoparticles grown on Cu nanowires (RhCu NWs) catalyst, which achieves a faradaic efficiency (FE) of 92.6% in the electrocatalytic reduction of HMF to BHMF at -20 mA cm-2 with no degradation in performance after 8 cycles. Kinetic investigations and electron spin resonance (ESR) spectroscopy reveal that the incorporation of Rh accelerates the water dissociation and facilitates the generation of Hads. In situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) further demonstrates that the Rh component boosts the proportion of ordered weakly hydrogen-bonded water molecules on the catalyst surface, which is much easier to dissociate. The construction of an interfacial Hads-rich environment promotes the HMF intermediates binding with Hads to BMHF, thereby suppressing the formation of undesired dimers. This work demonstrates the promise of altering the interfacial water environment as a strategy to boost the electrosynthetic properties of biomass-derived products toward value-added outcomes.

Ultrafine Pt-based catalyst decorated with oxygenophilic Ni-sites accelerating alkaline H2O dissociation for efficient hydrogen evolution.

Although Pt is a widely adopted commercial catalyst for the hydrogen evolution reaction (HER), its practical application is greatly limited by its prohibitive cost and high energy barrier for H2O dissociation in alkaline media. Herein, an ultrafine Pt-based catalyst decorated with oxygenophilic Ni-sites is rationally designed and successfully synthesized with Pt5(GS)10 (HGS = l-reduced glutathione) nanocluster precursor. The optimized Ni-decorated Pt catalyst (Ni-Pt-C-500) with ultrafine nanoparticles (about 1.6 nm) exhibits a low overpotential (14.0 mV) at 10 mA cm-2 and a mild Tafel slope of 20.8 mV dec-1 in the HER, which is superior to its undecorated counterpart (Pt-C-500), the commercial 20 wt% Pt/C catalyst and most of the previously reported Pt-based electrocatalysts. Experimental observations and theoretical calculations indicate that H2O could be spontaneously adsorbed to Ni-sites of the Ni-Pt-C-500 catalyst. Mechanistic studies reveal that Ni-sites promote HER by accelerating the kinetic of H2O cleavage and optimizing the electronic structure of Pt. This work paves a new avenue for designing other ultrafine hybrid electrocatalysts based on metal nanoclusters to enhance catalytic reaction kinetics.

Titania-Supported Cu-Single-Atom Catalyst for Electrochemical Reduction of Acetylene to Ethylene at Low-Concentrations with Suppressed Hydrogen Evolution.

Electrochemical acetylene reduction (EAR) is a promising strategy for removing acetylene from ethylene-rich gas streams. However, suppressing the undesirable hydrogen evolution is vital for practical applications in acetylene-insufficient conditions. Herein, Cu single atoms are immobilized on anatase TiO2 nanoplates (Cu-SA/TiO2 ) for electrochemical acetylene reduction, achieving an ethylene selectivity of ≈97% with a 5 vol% acetylene gas feed (Ar balance). At the optimal Cu-single-atom loading, Cu-SA/TiO2 is able to effectively suppress HER and ethylene over-hydrogenation even when using dilute acetylene (0.5 vol%) or ethylene-rich gas feeds, delivering a 99.8% acetylene conversion, providing a turnover frequency of 8.9 × 10-2  s-1 , which is superior to other EAR catalysts reported to date. Theoretical calculations show that the Cu single atoms and the TiO2 support acted cooperatively to promote charge transfer to adsorbed acetylene molecules, whilst also inhibiting hydrogen generation in alkali environments, thus allowing selective ethylene production with negligible hydrogen evolution at low acetylene concentrations.

Modulating Water Splitting Kinetics via Charge Transfer and Interfacial Hydrogen Spillover Effect for Robust Hydrogen Evolution Catalysis in Alkaline Media.

Designing and synthesizing advanced electrocatalysts with superior intrinsic activity toward hydrogen evolution reaction (HER) in alkaline media is critical for the hydrogen economy. Herein, a novel Ir@Rhene heterojunction electrocatalyst is synthesized via epitaxially confining ultrasmall and low-coordinate Ir nanoclusters on the ultrathin Rh metallene accompanying the formation of Ir/IrO2 Janus nanoparticles. The as-prepared heterojunctions display outstanding alkaline HER activity, with an overpotential of only 17 mV at 10 mA cm-2 and an ultralow Tafel slope of 14.7 mV dec-1 . Both structural characterizations and theoretical calculations demonstrate that the Ir@Rhene heterointerfaces induce charge density redistribution, resulting in the increment of the electron density around the O atoms in the IrO2 site and thus delivering much lower water dissociation energy. In addition, the dual-site synergetic effects between IrO2 and Ir/Rh interface trigger and improve the interfacial hydrogen spillover, thereby subtly avoiding the steric blocking of the active site and eventually accelerating the alkaline HER kinetics.

Origin of Limiting and Overlimiting Currents in Bipolar Membranes.

Bipolar membranes (BPMs), a special class of ion exchange membranes with the unique ability to electrochemically induce either water dissociation or recombination, are of growing interest for environmental applications including eliminating chemical dosage for pH adjustment, resource recovery, valorization of brines, and carbon capture. However, ion transport within BPMs, and particularly at its junction, has remained poorly understood. This work aims to theoretically and experimentally investigate ion transport in BPMs under both reverse and forward bias operation modes, taking into account the production or recombination of H+ and OH-, as well as the transport of salt ions (e.g., Na+, Cl-) inside the membrane. We adopt a model based on the Nernst-Planck theory, that requires only three input parameters─membrane thickness, its charge density, and pK of proton adsorption─to predict the concentration profiles of four ions (H+, OH-, Na+, and Cl-) inside the membrane and the resulting current-voltage curve. The model can predict most of the experimental results measured with a commercial BPM, including the observation of limiting and overlimiting currents, which emerge due to particular concentration profiles that develop inside the BPM. This work provides new insights into the physical phenomena in BPMs and helps identify optimal operating conditions for future environmental applications.

Boosting Alkaline Hydrogen Evolution Reaction through Water Structure Manipulation.

In the past, the design of efficient electrocatalyst materials for alkaline hydrogen evolution reaction (HER) was mostly focused on tuning the adsorption properties of reaction intermediates. A recent breakthrough shows that the performance can be improved by manipulating water structure at the electrode-electrolyte interface using atomically localized electric fields. The new approach was realized by using IrRu dizygotic single-atom sites and led to a significantly accelerated water dissociation and an overall improved alkaline HER performance. Supported by extensive data from advanced modeling, characterization, and electrochemical measurements, the work delivers an intricate examination of the interaction between water molecules and the catalyst surface, thereby enriching our understanding of water dissociation kinetics and offering new insights to boost overall alkaline HER efficiency.

Ni-CeO2 Heterostructure Promotes Hydrogen Evolution Reaction via Tuning of the O-H Bond Length of Adsorbed Water at the Electrolyte/Electrode Interface.

Understanding the properties and structure of reactant water molecules at the electrolyte solution/electrode interface is relevant to know the mechanisms of hydrogen evolution reaction (HER). However, this approach has rarely been implemented due to the elusive local microenvironment in the vicinity of the catalyst. Taking the Ni-CeO2 heterostructure immobilized onto carbon paper (Ni-CeO2 /CP) as a model, the dynamic behavior of adsorbed intermediates during the reaction was measured by in situ surface-enhanced infrared absorption spectroscopy with attenuated total reflection configuration (ATR-SEIRAS). Theoretical calculations are used in combination to comprehend the potential causes of increased HER activity. The results show that the O-H bond of adsorbed water at the electrolyte solution/electrode interface becomes longer for promoting the dissociation of water and accelerating the kinetically slow Volmer step. In addition, forming the Ni-CeO2 heterostructure interface optimizes the hydrogen adsorption Gibbs free energy, thus increasing HER activity. Therefore, the Ni-CeO2 /CP electrode exhibits remarkably low HER overpotentials of 37 and 119 mV at 10 and 100 mA cm-2 , which are close to commercial Pt/C (16 and 102.6 mV, respectively).