Accelerating Water Dissociation Research Articles

Promoting Water Activation via Molecular Engineering Enables Efficient Asymmetric C-C Coupling during CO2 Electroreduction.

Water activation plays a crucial role in CO2 reduction, but improving the electrocatalytic performance through controlled water activation presents a significant challenge. Herein, we achieved electrochemical CO2 reduction to ethene and ethanol with high selectivity by promoting water dissociation and asymmetric C-C coupling by engineering Cu surfaces with N-H-rich molecules. Direct spectroscopic evidence, coupled with density functional theory calculations, demonstrates that the N-H-rich molecules accelerate interfacial water dissociation via hydrogen-bond interactions, and the generated hydrogen species facilitate the conversion of *CO to *CHO. This enables the efficient asymmetric *CHO-*CO coupling to C2 products with a faradaic efficiency (FE) ∼ 30% higher than that of the unmodified catalyst. Moreover, by adjustment of the relative *CHO/*CO coverage via Cu surface facet regulation, the selectivity can be entirely switched between C2 products and CH4. These mechanistic insights further guided the development of a more efficient catalyst by directly modifying Cu2O nanocubes with the N-H-rich molecule, achieving remarkable C2 product (mainly ethene and ethanol) FEs of 85.7% at a current density of 800 mA cm-2 and excellent stability under nearing industrial conditions. This study advances our understanding of the CO2 reduction mechanisms and offers an effective and general strategy for enhancing electrocatalytic performance by accelerating water dissociation.

Ampere-Level Hydrogen Generation via 1000 H Stable Seawater Electrolysis Catalyzed by Pt-Cluster-Loaded NiFeCo Phosphide.

Seawater electrolysis can generate carbon-neutral hydrogen but its efficiency is hindered by the low mass activity and poor stability of commercial catalysts at industrial current densities. Herein, Pt nanoclusters are loaded on nickel-iron-cobalt phosphide nanosheets, with the obtained Pt@NiFeCo-P electrocatalyst exhibiting excellent hydrogen evolution reaction (HER) activity and stability in alkaline seawater at ampere-level current densities. The catalyst delivers an ultralow HER overpotential of 19.7mV at -10mA cm-2 in seawater-simulating alkaline solutions, along with a Pt-mass activity 20.8 times higher than Pt/C under the same conditions, while dropping to 8.3mV upon a five-fold NaCl concentrated natural seawater. Remarkably, Pt@NiFeCo-P offers stable operation for over 1000 h at 1 A cm-2 in an alkaline brine electrolyte, demonstrating its potential for efficient and long-term seawater electrolysis. X-ray photoelectron spectroscopy (XPS), in situ electrochemical impedance spectroscopy (EIS), and in situ Raman studies revealed fast electron and charge transfer from the NiFeCo-P substrate to Pt nanoclusters enabled by a strong metal-support interaction, which increased the coverage of H* and accelerated water dissociation on high valent Co sites. This study represents a significant advancement in the development of efficient and stable electrocatalysts with high mass activity for sustainable hydrogen generation from seawater.

Manipulation in local coordination of platinum single atom enables ultrahigh mass activity toward hydrogen evolution reaction

Atomic-engineering of noble metal into single-atom electrocatalysts with well-defined active sites has been considered as an effective approach to enhance the mass-activity towards hydrogen evolution reaction (HER), crucial for the practical implementation of this sustainable technology. Herein, we devise a metallic-coordination strategy via a facile one-step pyrolysis method, for the atomic isolation of a small amount of platinum (Pt, 0.45 wt%) atoms in the surface of nickel (Ni) nanoparticles (Pt1@Ni) encapsulated into nitrogen-doped carbon nanotubes (Pt1@Ni/NCNT). Such a Pt1@Ni/NCNT single-atom alloy catalyst exhibits a record-high and all-round superior HER performance including mass-activity (up to 350.7 A mgPt−1@η150), stability (>50 h at 100 mA cm−2), pH-tolerance by comparison with Pt1@NC. Our density functional theory calculations combined with in situ Raman spectroscopic studies reveal a synergistic dual-active-site catalytic mechanism, involving the fast hydrogen spillover effect on coordinated Ni supports and accelerated water dissociation in acidic and alkaline medium, respectively. A strong electronic hybridization of 5d orbital of alloyed Pt and 3d orbital of Ni atoms modulates the d band center of Pt, which not only boosts HER activity but also stabilizes Pt single atoms. Due to the double protecting strategy from strong anchoring effect in Ni support and chemically stable NCNT shell, a robust stability is achieved for Pt1@Ni/NCNT hierarchal catalyst. Our findings open up a new avenue to substantially tailor the activity of surface Pt atoms for the design of highly efficient and durable noble metal-based catalysts.

Ru-doped Mo2C grown on coconut shell derived 3D hierarchical carbon as robust electrocatalysts for hydrogen evolution reaction

Biomass, as a low-cost, environmental friendly and renewable carbon source with natural porous structure can be used as carriers. Molybdenum carbide (Mo2C), possessing metallic characteristics and a platinum-like d-band electronic structure, has recently emerged as promising candidate for hydrogen evolution reaction (HER). In this study, we fabricate a new electrocatalyst by embedding ruthenium (Ru) into Mo2C on carbonized coconut shell (Ru-Mo2C@CSC). Doping of Ru into Mo2C significantly activates the inherent HER activity by altering the surface state, which enhances electron accumulation and transfer between the intermediate and electrocatalyst surface. The obtained Ru-Mo2C@CSC exhibit a remarkably low overpotential of 40 mV at 10 mA cm−2 in 1 M KOH, matching the benchmark Pt/C. Both experimental and density functional theory (DFT) reveal that this outstanding electrocatalytic activity stems from its unique three-dimensional (3D) architecture and the altered electronic structure by Ru-doping. The distinct 3D hierarchical porous structure aids electrolyte penetration, increases exposure of active sites, and facilitates the release of gas products. Substituting Ru atoms notably diminish the proton adsorption strength at the Mo and C atom coordination sites and electronic modification of Mo by charge transfer from Ru to Mo which was observed by X-ray photoelectron spectroscopy. A synergetic interaction at the Ru-Mo interface is generated to optimize the adsorption–desorption energetics toward H intermediate and accelerate water dissociation.

Copper restructured transition metal/metal oxide heterostructure with a hierarchical nanostructure for accelerated water dissociation kinetics and alkaline hydrogen evolution

The slow kinetics of water dissociation on electrocatalysts lacking platinum hinders the advancement of cost-effective hydrogen production via alkaline water electrolysis. Herein, a hierarchically peach-flower-shaped electrocatalyst consisting of copper-restructured cobalt–nickel/cobalt–nickel oxide heterostructure anchored on copper nanowires (Cu-CoNiO/CoNi@Cu NWs) is developed for efficient hydrogen evolution reaction (HER). Benefiting from the optimized electronic configuration and geometric structure, this Cu-CoNiO/CoNi@Cu NWs catalyst performs an outstanding alkaline HER activity of 29 mV at 10 mA cm−2 and 98 mV at 100 mA cm−2, which is comparable with the state-of-the-art Pt/C catalyst (26 mV at 10 mA cm−2 and 117 mV at 100 mA cm−2). Our findings rank among the topmost catalytic efficiencies when compared to all previously reported non-noble metal catalysts and numerous noble metal catalysts. The combined experimental exploration and theoretical studies reveal that the incorporation of Cu dopant into CoNiO/CoNi heterostructure enhances electron transfer from metal atoms to O atom, leading to the formation of the polarized electric field to accelerate water dissociation and H evolution, eventually facilitating the overall alkaline HER process. The boosted electron exchange and mass transportation deriving from the introduction of Cu NWs and hierarchically peach-flower-shaped nanostructure further reinforce the HER activity of the Cu-CoNiO/CoNi catalyst.

Expediting catalytic performance and water resistance of toluene decomposition over MnOx through alkali metal doping induced electronic modulation

Achieving rapid ring–opening is considered the rate–limiting step in toluene oxidation, with water vapor having a positive effect on this objective. Herein, we propose a novel strategy for preparing K/MnOx catalyst by means of a secondary hydrothermal approach, capable of reducing the generation of intermediates and fosters a positive feedback loop in toluene oxidation by accelerating water dissociation. As indicated by characterizations, the presence of K not only effectively promotes the generation of reactive oxygen species and Mn3+ by expediting the electron transfer between Mn and O species but also act as a dopant to create more oxygen vacancies and therefore boosting the catalytic performance. Interestingly, despite competing adsorption of water molecules with toluene, the excellent water dissociation capability of K/MnOx creates a reactive oxygen species–rich surrounding. This environment facilitates ring cleavage stemming and ensures low–temperature oxidation of toluene simultaneously. The present study provides a new insight into the practical use of Mn–based catalysts for toluene decomposition.

Efficient ethylene electrosynthesis by accelerating water dissociation

Efficient ethylene electrosynthesis by accelerating water dissociation

Strategies for Tuning Tensile Strain and Localized Electrons in a Mo‐Doped NiCoCu Alloy for Enhancing Ampere‐Level Current Density HER Performance

AbstractDeveloping high‐activity non‐noble metal catalysts for improving the ability of water dissociation and H* adsorption/desorption in the hydrogen evolution reaction (HER) process in alkaline and neutral electrolytes is essential but remains challenging. Herein, a Mo‐doped NiCoCu alloy with tuned tensile strain and localized electrons is designed and synthesized by combining the solvothermal and annealing methods for achieving ampere‐level HER performance. Theoretical calculation results prove that Mo doping induces lattice tensile strain and localized electrons (electrons from Mo to the Ni/Co/Cu atoms), promoting the adsorption of O* and H* from H2O molecules on the Mo and Co sites and accelerating water dissociation. Therefore, NiCoCu‐Mo0.078/CF (CF = copper foam) shows low water dissociation energy, providing sufficient H* during the HER process. Meanwhile, its H* Gibbs free energy value is near zero, implying a rapid H* adsorption/desorption process. Electrochemical results show that NiCoCu‐Mo0.078/CF achieves better HER intrinsic activity in both a 1.0 m KOH (η−10 /η−1000 = 35/212 mV) and a 1.0 m phosphate buffer solution (η−10 /η−1000 = 24/256 mV) compared to NiCoCu‐Mo0/CF and NiCoCu‐Mo0.163/CF, and it can continuously operate for 100 h at −1000 mA cm−2. This work shows a sustainable way to design high‐performance catalysts for water electrolysis and proposes a well‐performing HER catalyst.

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.

Coupling Interaction between Precisely Located Pt Single‐Atoms/Clusters and NiCo‐Layered Double Oxide to Boost Hydrogen Evolution Reaction

AbstractCatalysts based on Pt single atom (SA) on metal oxides have shown tremendous potentials for alkaline hydrogen evolution reaction (HER), but they are severely limited by insufficient electron interactions of Pt sites and supports. Herein, a new methodology is developed to precisely locate Pt SAs and Pt clusters into NiCo layered double oxide (LDO) nanosheets, achieved using a dual‐ion etching process with subsequent phase transformation method. Uniquely, the Pt SAs are inserted into LDO layers to form Pt─Co bonds by occupying partial Ni positions, significantly strengthening electron interactions with NiCo LDO and promoting activity of HER. Results from density functional theory calculations indicate that the H* species are preferentially absorbed onto O sites on top of these Pt SAs, which are coupled with their adjacent Pt clusters to accelerate water dissociation in the Volmer step. As‐obtained Pt─NiCo LDO exhibits a low overpotential of 92 mV at 10 mA cm−2 and a Tafel slope of 73 mV dec−1, an excellent stability over 105 hours at 60 mA cm−2, and its mass activity is 6 times higher than commercial 20% Pt/C. This study highlights essential functions of coupling interactions between Pt SAs/clusters and LDOs to boost HER for hydrogen energy production.

Bipolar Membrane Seawater Splitting for Hydrogen Production: A Review.

The growing demand for clean energy has spurred the quest for sustainable alternatives to fossil fuels. Hydrogen has emerged as a promising candidate with its exceptional heating value and zero emissions upon combustion. However, conventional hydrogen production methods contribute to CO2 emissions, necessitating environmentally friendly alternatives. With its vast potential, seawater has garnered attention as a valuable resource for hydrogen production, especially in arid coastal regions with surplus renewable energy. Direct seawater electrolysis presents a viable option, although it faces challenges such as corrosion, competing reactions, and the presence of various impurities. To enhance the seawater electrolysis efficiency and overcome these challenges, researchers have turned to bipolar membranes (BPMs). These membranes create two distinct pH environments and selectively facilitate water dissociation by allowing the passage of protons and hydroxide ions, while acting as a barrier to cations and anions. Moreover, the presence of catalysts at the BPM junction or interface can further accelerate water dissociation. Alongside the thermodynamic potential, the efficiency of the system is significantly influenced by the water dissociation potential of BPMs. By exploiting these unique properties, BPMs offer a promising solution to improve the overall efficiency of seawater electrolysis processes. This paper reviews BPM electrolysis, including the water dissociation mechanism, recent advancements in BPM synthesis, and the challenges encountered in seawater electrolysis. Furthermore, it explores promising strategies to optimize the water dissociation reaction in BPMs, paving the way for sustainable hydrogen production from seawater.

Titanium Dioxide and N-Doped Carbon Hybrid Nanofiber Modulated Ru Nanoclusters for High-Efficient Hydrogen Evolution Reaction Electrocatalyst.

The designing and fabricating highly active hydrogen evolution reaction (HER) electrocatalysts that can superior to Pt/C is extremely desirable but challenging. Herein, the fabrication of Ru/TiO2/N-doped carbon (Ru/TiO2/NC) nanofiber is reported as a novel and highly active HER electrocatalyst through electrospinning and subsequent pyrolysis treatment, in which Ru nanoclusters are dispersed into TiO2/NC hybrid nanofiber. As a novel support, experimental and theoretical calculation results reveal that TiO2/NC can more effectively accelerate water dissociation as well as optimize the adsorption strength of *H than TiO2 and NC, thus leading to a significantly enhanced HER activity, which merely requires an overpotential of 18mV to reach 10mAcm-2, outperforming Pt/C in an alkaline solution. The electrolytic cell composed of Ru/TiO2/NC nanofiber and NiFe LDH/NF can generate 500 and 1000mAcm-2 at voltages of 1.631 and 1.753V, respectively. Furthermore, the electrolytic cell also exhibits remarkable durability for at least 100h at 200mAcm-2 with negligible degradation in activity. The present work affords a deep insight into the influence of support on the activity of electrocatalyst and the strategy proposed in this research can also be extended to fabricate various other types of electrocatalysts for diverse electrocatalytic applications.

Accelerating water dissociation at hierarchical nanostructured electrocatalyst for efficient hydrogen evolution

The sluggish kinetics of the water electrolysis reaction is a key issue for hydrogen production, so the rational design of a high-efficiency hydrogen evolution reaction (HER) electrocatalyst with various structures has attracted extensive attention. Herein, a coaxial hierarchical three-dimensional (3D) nanostructure, Pt@Mo–S–Ni-CNTs, was prepared. In this nanostructure, carbon nanotubes (CNTs) as the core, Mo–S–Ni ultrathin nanosheets as shells, and ultrasmall metal nanoparticles (NPs) were grown uniformly on the surface of Mo–S–Ni nanosheets (NSs). At a current density of 10 mA m−2, the catalyst under investigation has remarkable hydrogen evolution reaction (HER) activity under acidic conditions. The overpotential (η10) is measured to be 61.2 mV, while the Tafel slope is determined to be 40.2 mV dec−1. Meanwhile, in an alkaline medium, η10 is 80.5 mV and the Tafel slope is 52.3 mV dec−1. It also shows great mass activities of 1.32 A mg−1 and 1.86 A mg−1, which are higher than those of commercial Pt/C HER catalysts. Impressively, the excellent HER activity and durability of Pt@Mo–S–Ni-CNTs are mainly attributed to the close binding effects among Pt, MoS2, and NiS. Theoretical simulations show that the MoS2/NiS interfaces facilitate H2O dissociation and that Platinum (Pt) enhances the absorption of hydrogen atoms (H) and increases the charge transfer kinetics of the Mo–S–Ni, thus significantly improving the HER activity. This work highlights the importance of engineering interface nanosheets based on transition-metal dichalcogenides for enhanced HER performance.

Alleviating OH Blockage on the Catalyst Surface by the Puncture Effect of Single-Atom Sites to Boost Alkaline Water Electrolysis.

Nonprecious transition metal catalysts have emerged as the preferred choice for industrial alkaline water electrolysis due to their cost-effectiveness. However, their overstrong binding energy to adsorbed OH often results in the blockage of active sites, particularly in the cathodic hydrogen evolution reaction. Herein, we found that single-atom sites exhibit a puncture effect to effectively alleviate OH blockades, thereby significantly enhancing the alkaline hydrogen evolution reaction (HER) performance. Typically, after anchoring single Ru atoms onto tungsten carbides, the overpotential at 10 mA·cm-2 is reduced by more than 130 mV (159 vs 21 mV). Also, the mass activity is increased 16-fold over commercial Pt/C (MA100 = 17.3 A·mgRu-1 vs 1.1 A·mgPt-1, Pt/C). More importantly, such electrocatalyst-based alkaline anion-exchange membrane water electrolyzers can exhibit an ultralow potential (1.79 Vcell) and high stability at an industrial current density of 1.0 A·cm-2. Density functional theory (DFT) calculations reveal that the isolated Ru sites could weaken the surrounding local OH binding energy, thus puncturing OH blockage and constructing bifunctional interfaces between Ru atoms and the support to accelerate water dissociation. Our findings exhibit generality to other transition metal catalysts (such as Mo) and contribute to the advancement of industrial-scale alkaline water electrolysis.

Ru incorporated into Se vacancy-containing CoSe2 as an efficient electrocatalyst for alkaline hydrogen evolution.

In alkaline media, slow water dissociation leads to poor overall hydrogen evolution performance. However, Ru catalysts have a certain water dissociation performance, thus regulating the Ru-H bond through vacancy engineering and accelerating water dissociation. Herein, an excellent Ru-based electrocatalyst for the alkaline HER has been developed by incorporating Ru into Se vacancy-containing CoSe2 (Ru-VSe-CoSe2). The results from X-ray photoelectron spectroscopy, kinetic isotope effect, and cyanide poisoning experiments for four catalysts (namely Ru-VSe-CoSe2, Ru-CoSe2, VSe-CoSe2, and CoSe2) reveal that Ru is the main active site in Ru-VSe-CoSe2 and the presence of Se vacancies greatly facilitates electron transfer from Co to Ru via a bridging Se atom. Thus, electron-rich Ru is formed to optimize the adsorption strength between the active site and H*, and ultimately facilitates the whole alkaline HER process. Consequently, Ru-VSe-CoSe2 exhibits an excellent HER activity with an ultrahigh mass activity of 44.2 A mgRu-1 (20% PtC exhibits only 3 A mgRu-1) and a much lower overpotential (29 mV at 10 mA cm-2) compared to Ru-CoSe2 (75 mV), VSe-CoSe2 (167 mV), CoSe2 (190 mV), and commercial Pt/C (41 mV). In addition, the practical application of Ru-VSe-CoSe2 is illustrated by designing a Zn-H2O alkaline battery with Ru-VSe-CoSe2 as the cathode catalyst, and this battery shows its potential application with a maximum power density of 4.9 mW cm-2 and can work continuously for over 10 h at 10 mA cm-2 without an obvious decay in voltage.

Integrated PtxCoy-Hierarchical Carbon Matrix Electrocatalyst for Efficient Hydrogen Evolution Reaction.

Pt-based catalysts are regarded as state-of-the-art electrocatalysts for producing clean hydrogen energy; however, their wide application is restricted by their low abundance, high cost, and poor stability. Herein, we report an integrated PtxCoy-hierarchical carbon matrix electrocatalyst (Pt/Co@NCNTs, Pt3Co@NCNTs, PtCo@NCNTs, and PtCo3@NCNTs) that is developed using a thermally driven Co migration strategy forming alloy nanoparticles to achieve efficient hydrogen evolution reaction (HER). Benefiting from its electronic regulation effect and unique hierarchical hollow structure, the Pt3Co@NCNTs catalyst loaded with 11.5 wt % Pt exhibits superior catalytic performance and durability for HER compared with commercial 20 wt % Pt/C. Under both alkaline and acidic conditions, Pt3Co@NCNTs exhibits excellent HER activity with overpotentials of 21 and 45 mV at 10 mA cm-2, respectively. Density functional theory (DFT) results further verify that the interaction between Pt and Co in Pt3Co@NCNTs can modulate electronic rearrangement, optimize the d-band center, and accelerate water dissociation and *H desorption, thereby enhancing HER activity.

Light-driven assembly of Pt clusters on Mo-NiOx nanosheets to achieve Pt/Mo-NiOx hybrid with dense heterointerfaces and optimized charge redistribution for alkaline hydrogen evolution

Designing cost-effective alkaline hydrogen evolution reaction (HER) catalysts with high water dissociation ability, enhanced hydroxyl transfer rate and optimized hydrogen adsorption free energy (ΔGH*) by a time and energy efficient strategy is pivotal, but still challenging for alkaline water electrolysis. Herein, Pt/Mo-NiOx hybrid consisting of Pt clusters assembled on Mo-doped NiOx nanosheet arrays is prepared on the surface of raw NiMo foam (NMF) by a light-driven strategy to address this challenge. Benefitting from the electronic interaction between Mo-NiOx and Pt, the Pt/Mo-NiOx composite owns optimized ΔGH* and is beneficial for accelerating water dissociation and hydroxyl transfer. As a result, the optimized Pt/Mo-NiOx/NMF electrode displays an exceptional alkaline HER activity with a low overpotential of 62 mV to obtain 100 mA cm−2 and a high Pt mass activity (13.2 times as high as that of commercial 20 wt% Pt/C). Furthermore, the assembled two-electrode cell of Pt/Mo-NiOx/NMF||NiFe-LDH/NF requires a voltage of only 1.549 V to deliver 100 mA cm−2, along with negligible activity decay after 70 h stability test. The present study provides a promising strategy for exploiting high-performance electrocatalysts towards alkaline HER.

Favoring CO Intermediate Stabilization and Protonation by Crown Ether for CO2 Electromethanation in Acidic Media.

The large-scale deployment of CO2 electroreduction is hampered by deficient carbon utilization in neutral and alkaline electrolytes due to CO2 loss into (bi)carbonates. Switching to acidic media mitigates carbonation, but suffers from low product selectivity because of hydrogen evolution. Here we report a crown ether decoration strategy on a Cu catalyst to enhance carbon utilization and selectivity of CO2 methanation under acidic conditions. Macrocyclic 18-Crown-6 is found to enrich potassium cations near the Cu electrode surface, simultaneously enhancing the interfacial electric field to stabilize the *CO intermediate and accelerate water dissociation to boost *CO protonation. Remarkably, the mixture of 18-Crown-6 and Cu nanoparticles affords a CH4 Faradaic efficiency of 51.2 % and a single pass carbon efficiency of 43.0 % toward CO2 electroreduction in electrolyte with pH=2. This study provides a facile strategy to promote CH4 selectivity and carbon utilization by modifying Cu catalysts with supramolecules.

Favoring CO Intermediate Stabilization and Protonation by Crown Ether for CO2 Electromethanation in Acidic Media

AbstractThe large‐scale deployment of CO2 electroreduction is hampered by deficient carbon utilization in neutral and alkaline electrolytes due to CO2 loss into (bi)carbonates. Switching to acidic media mitigates carbonation, but suffers from low product selectivity because of hydrogen evolution. Here we report a crown ether decoration strategy on a Cu catalyst to enhance carbon utilization and selectivity of CO2 methanation under acidic conditions. Macrocyclic 18‐Crown‐6 is found to enrich potassium cations near the Cu electrode surface, simultaneously enhancing the interfacial electric field to stabilize the *CO intermediate and accelerate water dissociation to boost *CO protonation. Remarkably, the mixture of 18‐Crown‐6 and Cu nanoparticles affords a CH4 Faradaic efficiency of 51.2 % and a single pass carbon efficiency of 43.0 % toward CO2 electroreduction in electrolyte with pH=2. This study provides a facile strategy to promote CH4 selectivity and carbon utilization by modifying Cu catalysts with supramolecules.

Boosting Photocatalytic Hydrogen Evolution Activity by Accelerating Water Dissociation over Rh/Zn(OH)2 Catalyst in Alkaline Solution

Boosting Photocatalytic Hydrogen Evolution Activity by Accelerating Water Dissociation over Rh/Zn(OH)₂ Catalyst in Alkaline Solution