Competitive Reaction Research Articles

Reductive Transformation of CO2 to Organic Compounds

AbstractCarbon dioxide is a major greenhouse gas and a safe, abundant, easily accessible, and renewable C1 resource that can be chemically converted into high value‐added chemicals, fuels and materials. The preparation of urea, organic carbonates, salicylic acid, etc. from CO2 through non‐reduction conversion has been used in industrial production, while CO2 reduction transformation has become a research hotspot in recent years due to its involvement in energy storage and product diversification. Designing suitable catalysts to achieve efficient and selective conversion of CO2 is crucial due to its thermodynamic stability and kinetic inertness. From this perspective, the redistribution of charges within CO2 molecules through the interaction of Lewis acid/base or metal complexes with CO2, or the forced transfer of electrons to CO2 through photo‐ or electrocatalysis, is a commonly used effective way to activate CO2. Based on understanding of the activation/reaction mechanism on a molecular level, we have developed metal complexes, metal salts, inorganic/organic salts, ionic liquids, as well as nitrogen rich and porous materials as efficient catalysts for CO2 reductive conversions. The goal of this personal account is to summarize the catalytic processes of CO2 reductive conversion that have been developed in the past 7 years: 1) For the reductive functionalization of CO2, the major challenge lies in accurately adjusting reaction parameters (such as pressure) to achieve high catalytic efficiency and the product selectivity; 2) For photocatalytic or electrocatalytic reduction of CO2, how to suppress competitive hydrogen evolution reactions and improve catalyst stability are key points that requires continuous attention.

Isolated FeN3 sites anchored hierarchical porous carbon nanoboxes for hydrazine‐assisted rechargeable Zn‐CO2 batteries with ultralow charge voltage

AbstractZn‐CO2 batteries (ZCBs) are promising for CO2 conversion and electric energy release. However, the ZCBs couple the electrochemical CO2 reduction (ECO2R) with the oxygen evolution reaction and competitive hydrogen evolution reaction, which normally causes ultrahigh charge voltage and CO2 conversion efficiency attenuation, thereby resulting in ~90% total power consumption. Herein, isolated FeN3 sites encapsulated in hierarchical porous carbon nanoboxes (Fe‐HPCN, derived from the thermal activation process of ferrocene and polydopamine‐coated cubic ZIF‐8) were proposed for hydrazine‐assisted rechargeable ZCBs based on ECO2R (discharging process: CO2 + 2H+ → CO + H2O) and hydrazine oxidation reaction (HzOR, charging process: N2H4 + 4OH− → N2 + 4H2O + 4e−). The isolated FeN3 endows the HzOR with a lower overpotential and boosts the ECO2R with a 96% CO Faraday efficiency (FECO). Benefitting from the bifunctional ECO2R and HzOR catalytic activities, the homemade hydrazine‐assisted rechargeable ZCBs assembled with the Fe‐HPCN air cathode exhibited an ultralow charge voltage (decreasing by ~1.84 V), excellent CO selectivity (FECO close to 100%), and high 89% energy efficiency. In situ infrared spectroscopy confirmed that Fe‐HPCN can generate rate‐determining *N2 and *CO intermediates during HzOR and ECO2R. This paper proposes FeN3 centers for bifunctional ECO2R/HzOR performance and further presents the pioneering achievements of ECO2R and HzOR for hydrazine‐assisted rechargeable ZCBs.

Indium Oxide Layer Dual Functional Modified Bismuth Vanadate Photoanode Promotes Photoelectrochemical Oxidation of Water to Hydrogen Peroxide.

The photoelectrochemical (PEC) dual-electron pathway for water oxidation to produce hydrogen peroxide (H2O2) shows promising prospects. However, the dominance of the four-electron pathway leading to O2 evolution competes with this reaction, severely limiting the efficiency of H2O2 production. Here, we report a In2O3 passivator-coated BiVO4 (BVO) photoanode, which effectively enhances the selectivity and yield of H2O2 production via PEC water oxidation. Based on XPS spectra and DFT calculations, a heterojunction is formed between In2O3 and BVO, promoting the effective separation of interface and surface charges. More importantly, Mott-Schottky analysis and open-circuit potential measurements demonstrate that the In2O3 passivation layer on the BVO photoanode shifts the hole quasi-Fermi level towards the anodic direction, enhancing the oxidation level of holes. Additionally, the widening of the depletion layer and the flattening of the band bending on the In2O3-coated BVO photoanode favor the generation of H2O2 while suppressing the competitive O2 evolution reaction. In addition, the coating of In2O3 can also inhibit the decomposition of H2O2 and improve the stability of the photoanode. This work provides new perspectives on regulating PEC two/four-electron transfer for selective H2O2 production via water oxidation.

Controllable Synthesis of BixOyBrz/TiO2 Heterojunctions with Excellent Visible‐Light‐Driven Photocatalytic Activities for Phenol

AbstractBixOyBrz/TiO2 composites have been synthesized by hydrothermal method, with TiO2 nanoparticles being employed as substrate. During the process of hydrothermal reaction, both temperature and pH have been utilized to effectively regulate the Bi/Br atomic ratio of BixOyBrz/TiO2 composites. In essence, the competitive reaction between OH− and Br− in the solution is the key factor to form BixOyBrz with different Bi/Br atomic ratios. Under visible light, the prepared Bi4O5Br2/TiO2 heterojunction demonstrates higher photocatalytic activity than other BixOyBrz/TiO2 composites for phenol and Rh B. The removal rate of phenol with Bi4O5Br2/TiO2 heterojunction is up to 92.1% after irradiation for 75 min. The excellent photocatalytic activities of Bi4O5Br2/TiO2 heterojunction are mainly attributed to its optimized microstructure and the matching band energy structure, whereby TiO2 nanoparticles with ≈10 nm diameter uniformly arranged on ≈10.2 nm thick Bi4O5Br2 nanosheets. Moreover, the heterojunction structure promotes the separation of photo‐generated electrons and holes in Bi4O5Br2/TiO2, while and h+ are the main active species during its photocatalytic processes.

Enhanced electrocatalytic C[sbnd]H amination of toluene via tailored interfacial microenvironment

Electrocatalytic CH amination of hydrocarbons is a promising avenue for the synthesis of high-value CN compounds. However, efficient activation of CH bonds remains a significant challenge in electrocatalytic CN coupling. Herein, we present a novel strategy to enhance the electrocatalytic conversion of toluene to N-benzylacetamide through a Ritter–type reaction by engineering a hydrophobic electrode–electrolyte interface using polytetrafluoroethylene (PTFE)-coated carbon paper (CP). The hydrophobic CP-based electrode exhibited a superior N-benzylacetamide productivity of 1860.9 mmol m−2h−1 and a substantially higher Faradaic efficiency (FE) of 70.1 % compared to pure CP (41.5 %). Experimental results and density functional theory (DFT) calculations reveal that the PTFE coating promotes toluene adsorption and efficiently lowers the energy barrier for toluene dehydrogenation. Additionally, the hydrophobic interface effectively hinders water adsorption on the electrode, suppressing the competitive water oxidation reaction. This study underscores the crucial role of interfacial engineering in optimizing electrocatalytic CN coupling reactions for the sustainable synthesis of high-value amide compounds.

Parallel (competitive) reactions of micelle formation and cyclodextrin–surfactant inclusion complex formation in aqueous solution: A consequence of the Gibbs–Duhem equation—invariance of the mass action law and the possibility of determining the equilibrium constant of the inclusion complex

The Gibbs–Duhem equation results in the independence between the standard Gibbs free energy of micelle formation and the standard Gibbs free energy of monocomponent surfactant’s and cyclodextrin’s (CD’s) inclusion complex formation in aqueous solution. The experimental data show that the surfactant’s critical micellar concentration increases in the presence of CD. At a constant temperature, the standard Gibbs free energy of micelle formation remains constant, irrespective of the presence of parallel competitive processes such as inclusion complex formation. This indicates that the critical micellar concentration remains unchanged at the corresponding concentration scale. As a result, the equilibrium constant for surfactant–CD inclusion complex formation can be determined by changing the critical micellar concentration in the presence and absence of CD. A graphical method for determining the equilibrium constant of the inclusion complex is also presented. An analytical approach for analyzing the influence of the formation of the inclusion complex with CD on the formation of the binary mixed micellar pseudophase is presented. Suppose that different values exist for the equilibrium constants of the formation of the inclusion complex for two surfactants from their binary mixture. In this case, there is a change in the initial mole fraction from the initial mixture of surfactants, which should be considered when applying the regular solution theory protocol when determining the parameters of a binary mixed micelle in the presence of CD.

Copper‐Catalyzed Enantioselective Dehydro‐Diels–Alder Reaction: Atom‐Economical Synthesis of Axially Chiral Carbazoles

AbstractThe dehydro‐Diels–Alder (DDA) reaction is a powerful method for the construction of aromatic compounds. However, the enantioselective DDA reaction has been rarely developed, probably due to the competitive thermal reaction. Herein, we report a copper‐catalyzed enantioselective DDA reaction through vinyl cation pathway. The reaction leads to the atom‐economical synthesis of axially chiral phenyl and indolyl carbazoles in generally excellent yields with good to excellent atroposelectivities. This methodology represents the first example of non‐noble metal‐catalyzed enantioselective DDA reaction. Notably, new chiral ligand and organocatalyst derived from the constructed axially chiral carbazole are demonstrated to be useful in asymmetric catalysis.

Mechanisms of efflorescence of alkali-activated slag

Efflorescence presents not only as a cosmetic concern but also as a structural issue, which impacts the performance of alkali-activated materials (AAMs). In this study, the mechanisms of efflorescence of alkali-activated slag (AAS) pastes are investigated. First, the efflorescence of AAS pastes with different alkali dosages (3 %, 5 % and 7 %), activator types (sodium hydroxide (NH) and sodium silicate (NS)), exposure atmospheres (ambient, N2 and 0.2 vol% CO2), and relative humidities (40 %, 60 % and 80 %) was observed. Subsequently, leaching tests were performed and the impacts of efflorescence on AAS pastes at different heights were studied. It was found that a lower relative humidity facilitated more rapid and severe efflorescence. The positioning of efflorescence products was dependent on the porosity of the matrix. Compared to NH pastes, NS pastes subjected to semi-contact water conditions were more vulnerable to cracking problems, which turned out to be exacerbated by the formation of efflorescence products. A new method to quantify efflorescence was developed and it corresponded well with both efflorescence observations and leaching experiments. Furthermore, a competitive reaction between Ca and Na in the presence of carbonate ions was identified. CaCO3, a representative product of natural carbonation, was rarely found in the regions where efflorescence products (sodium carbonate) formed. Regarding compressive strength, NS pastes were more adversely affected by efflorescence than NH pastes.

Responsive integration performed by laser-induced Er3+ structural doping and graphene nanoplatelets

Laser-induced preparation method has the advantages of high efficiency, high yield, no ionic diffusion restriction and competitive side reaction, which can prepare diversified composite materials based on small-scale and distributed characteristics. Besides, integrating multiple performance and conducting inductive feedback are helpful for the reliability and calibration of laser-induced materials in the precision field. Herein, responsive integration is designed based on graphene nanoplatelets/ZnSe:Er3+ composite with optical, electrical, thermal and visual properties for real-time feedback. Er3+ ions doped ZnSe is obtained by fast laser-induced method, combined with two-dimensional graphene nanoplatelets and assembled into temperature-sensitive polyimide and cellulose paper, realizing the characteristics of photoelectric conversion and photothermal conversion. Besides, red fluorescence guiding perceptual behavior can also be produced under the radiation of NIR laser. Based on the proposed composite, bionic flower is constructed, and exhibits good motion features in blooming. Meanwhile, large curvature bending, high thermal sensitivity and strong fluorescence emission are also revealed. Such performance combination design provides a convenient approach for multi signals cross feedback in soft actuator, which strengthens the monitoring and guidance of motion perceptions, and can be potentially applied in diversified fields.

Site-Selective Direct γ-Difunctionalization of Diazoenals: Application to the Synthesis of Enal-Functionalized Allenes and Furans.

A new approach for the synthetically important γ-functionalized enals has been developed. The strategy involves rhodium-catalyzed direct C-C & C-S bond forming site-selective γ-difunctionalization of diazoenals with aryl propargyl sulfides via sulfur ylide [2,3] sigmatropic rearrangement, resulting in the highly functionalized γ-allenyl(sulfanyl)enals in excellent yield at ambient temperature. This highly versatile approach constitutes a viable alternative to the remote carbonyl-directed γ-functionalization of unmodified enals which suffer from competitive side reactions. The synthetic utility of the γ-allenyl(sulfanyl)enals was demonstrated by the InCl3-catalyzed cycloisomerization to the trisubstituted furanyl-enals via an unusual 1,4-sulfanyl migration. In addition, an operationally simple and efficient one-pot [3+2] annulation of diazoenals and propargyl sulfides, involving combined γ-difunctionalization and cycloisomerization was successfully developed for the diverse enal-functionalized furans.

Synergistic Cationic Shielding and Anionic Chemistry of Potassium Hydrogen Phthalate for Ultrastable Zn─I2 Full Batteries.

Electrolyte additives are investigated to resolve dendrite growth, hydrogen evolution reaction, and corrosion of Zn metal. In particular, the electrostatic shielding cationic strategy is considered an effective method to regulate deposition morphology. However, it is very difficult for such a simple cationic modification to avoid competitive hydrogen evolution reactions, corrosion, and interfacial pH fluctuations. Herein, multifunctional additives of potassium hydrogen phthalate (KHP) based on the synergistic design of cationic shielding and anionic chemistry for ultrastable Zn||I2 full batteries are demonstrated. K cations, acting as electrostatic shielding cations, constructed the smooth deposition morphology. HP anions can enter the first solvation shell of Zn2+ for the reduced activities of H2O, while they remain in the primary solvation shell and are finally involved in the formation of SEI, thus accelerating the charge transfer kinetics. Furthermore, by in situ monitoring the near-surface pH of the Zn electrode, the KHP additives can effectively inhibit the accumulation of OH- and the formation of by-products. Consequently, the symmetric cells achieve a high stripping-plating reversibility of over 4500 and 2600 h at 1.0 and 5mA cm-2, respectively. The Zn||I2 full cells deliver an ultralong term stability of over 1400 cycles with a high-capacity retention of 78.5%.

Single and dual-atom catalysts towards electrosynthesis of ammonia and urea: a review.

Ammonia and urea represent two important chemicals that have contributed to the rapid development of humanity. However, their industrial production requires harsh conditions, consuming excessive energy and resulting in significant greenhouse gas emission. Therefore, there is growing interest in the electrocatalytic synthesis of ammonia and urea as it can be carried out under ambient conditions. Recently, atomic catalysts (ACs) have gained increased attention for their superior catalytic properties, being able to outperform their micro and nano counterparts. This review examines the advantages and disadvantages of ACs and summarises the advancement of ACs in the electrocatalytic synthesis of ammonia and urea. The focus is on two types of AC - single-atom catalysts (SACs) and diatom catalysts (DACs). SACs offer various advantages, including the 100% atom utilization that allows for low material mass loading, suppression of competitive reactions such as hydrogen evolution reaction (HER), and alternative reaction pathways allowing for efficient synthesis of ammonia and urea. DACs inherit these advantages, possessing further benefits of synergistic effects between the two catalytic centers at close proximity, particularly matching the NN bond for N2 reduction and boosting C-N coupling for urea synthesis. DACs also possess the ability to break the linear scaling relation of adsorption energy of reactants and intermediates, allowing for tuning of intermediate adsorption energies. Finally, possible future research directions using ACs are proposed.

Physicochemical Analysis of Cu(II)-Driven Electrochemical CO2 Reduction and its Competition with Proton Reduction.

The reduction of CO2 has become a key role in reducing greenhouse gas emissions in efforts to search for long-term responses to climate change. We report a a couple of CO2-reducing molecular catalysts based on earth-abundant copper complexes. These are [Cu(DPA)(PyNAP)] (1) and [Cu(DPA)(PyQl)] (2) (where, DPA = pyridine-2,6-dicarboxylic acid, PyNAP = 2-(pyridin-2-yl)-1,8-naphthyridine, and PyQl = 2-(pyridin-2-yl)quinoline). The copper metal-catalysed 2-electron reduction of CO2 to CO in the presence of 2-protons is challenging. These catalysts exhibit the production of CO gas in DMF/water mixtures, achieving an impressive faradaic efficiency of 84% and 72% for complex 1 and 2 at -1.7 V vs. SCE, respectively, for selective CO2 reduction. The production of H2 due to 2H+ + 2e- was also observed as a byproduct through the competitive proton reduction reaction. This was cross-verified by online gas and mass analysis.Our investigations confirmed the stability of the electrocatalysts under the electrocatalytic conditions. The mechanistic pathways were proposed to work with the EECC and ECEC (E: electrochemical and C: chemical) mechanisms. A CO2 insertion into an in-situ generated hydride from the Cu-center generates CO through the favourable path.

Harnessing in-situ oxidation of nanostructured mxene to modulate the electronic structure for improved selectivity for electrochemical carbon dioxide reduction

The electrochemical CO2 reduction reaction (CO2RR) is a promising approach to valorizing CO2. Ti3C2TX as a support material has received significant interest in enhancing CO2RR performance for tuning the electronic structure. However, there has been relatively less focus on changes to the Ti3C2TX electronic structure induced by loading catalysts onto the Ti3C2TX. Because Ti3C2TX has an intrinsic activity for both CO2RR and the competitive hydrogen evolution reaction (HER), electronic structure changes can affect the balance between CO2RR and HER selectivity. Therefore, tuning the electronic structure of Ti3C2TX can control the competition between CO2RR and HER and tune the selectivity and activity. Herein, we report that Ti3C2TX’s electronic structure can be tuned by the Ag+ loading method via redox interactions, tuning the reaction selectivity and activity for CO2RR. To illustrate this effect, we compare the CO2RR performance of in-situ formed Ag nanoparticles (NPs) on Ti3C2TX (0.9Ag-IS-Ti3C2TX) with physically mixed Ag NPs and Ti3C2TX (0.9Ag/P/Ti3C2TX). Here, ‘0.9’ refers to the molar ratio between Ag precursor and Ti3C2Tx, and ‘IS’ vs. ‘P’ refers to in-situ formed vs. physically mixed Ag NPs. 0.9Ag-IS-Ti3C2TX demonstrates a higher oxidation state for Ti and a higher proportion of Ti-O bonds than 0.9Ag/P/Ti3C2TX. Compared to 0.9Ag/P/Ti3C2TX, 0.9Ag-IS-Ti3C2TX exhibits higher CO Faradaic efficiency (FE), rising from 8.1 % with a partial current density of −2.0 mA cm−2 to 49.6 % with a partial current density of −20.1 mA cm−2 at −1.4 V vs. RHE (reversible hydrogen electrode). To harness this effect, we demonstrate control over the CO: H2 ratio of syngas formed from CO2RR over our Ti3C2TX-supported catalysts. Further electrochemical anodic oxidation experiments reveal the critical oxidation potential of Ti3C2TX (0.8 V vs. RHE) and show that HER can be partially suppressed by partial oxidation of Ti3C2TX. This work highlights the importance of considering the changes in Ti3C2TX (and other) supports when supporting catalysts for CO2RR and other electrochemical reactions.

Microenvironment Manipulation Strategies for Acidic CO2 Electrolysis

AbstractThe electrochemical reduction of CO2 (CO2RR) has gained significant attention due to its potential to reduce carbon emissions and produce valuable fuels and chemicals. CO2RR is typically carried out in neutral or alkaline conditions, while challenges such as the carbon crossover and salt precipitate can hinder the practical application. Conducting CO2RR in acidic media presents a promising method to address these issues, although it faces the problem of low efficiency and poor catalysis stability. Regulating the interface/surface microenvironment near the catalysts is crucial to minimize the competitive hydrogen evolution reaction and enhance CO2RR activity and long‐term stability. This review outlines recent advancements in acidic CO2RR, emphasizing various microenvironment engineering strategies for optimizing the CO2RR kinetics including electrolyte composition manipulation, catalyst design, electrode modification and cell configuration optimization. Additionally, the review addresses challenges into developing practical and cost‐effective CO2RR systems.

Triphasic Hydroxysilylation of Alkenes by Mechanically Piezoelectric Catalysis

AbstractThe 1,2‐hydroxysilylation of alkenes is crucial for synthesizing organosilicon compounds which are key intermediates in material science, pharmaceuticals, and organic synthesis. The development of strategies employing hydrogen atom transfer pathways is currently hindered by the existence of various competing reactions. Herein, we reported a novel mechanochemical strategy for the triphasic 1,2‐hydroxysilylation of alkenes through a single‐electron‐transfer pathway. Our approach not only circumvents competitive reactions to enable the first‐ever 1,2‐hydroxysilylation of unactivated alkenes but also pioneers the research in mechanic force‐induced triphasic reactions under ambient conditions. This gentle method offers excellent compatibility with various functional groups, operates under simple and solvent‐free conditions, ensures rapid reaction time. Preliminary mechanistic investigations suggest that silylboronate can be transformed to a silicon radical by highly polarized Li2TiO3 particles and oxygen under ball‐milling condition.

Localized heating coupling with radical oxidation eliminating antibiotic resistance genes (ARGs) in interfacial photothermal Fenton-like disinfection process

Conventional oxidative disinfection processes are inefficient in eliminating intracellular antibiotic resistance genes (iARGs) due to the barrier of the cell membrane and the competitive reaction of cellular constituents within antibiotic-resistant bacteria (ARB), resulting in the widespread prevalence of ARGs in recycled water. This study presented the first application of localized heating coupling with advanced oxidation to destroy the resistant Escherichia coli cells and improved subsequent iARGs (blaTEM-1) degradation in a novel photothermal Fenton-like disinfection process. The Fe-Mn@CNT microfiltration membrane, comprising carbon nanotubes wrapped with Fe and Mn nanoparticles (Fe-Mn@CNT), was employed as a nanomaterial for photothermal conversion and H2O2 activation. The highly efficient absorption of full-spectrum photons by CNTs enabled the Fe-Mn@CNT membrane to concentrate light to generate localized intense heat, resulting in the destruction of ARB nearby, and the subsequent release of iARGs. Interfacial heat favored Fe-Mn-induced H2O2 activation, leading to the production of more ·OH, which in turn promoted the oxidation for ARG degradation and ARB cell damage. The results of the acetylcysteine quenching experiments indicated that interfacial heating and radical oxidation-induced accumulation of intracellular reactive oxygen species contributed to the elimination of about 1-log iARGs through direct attack. The integrity of the cell membrane, the morphology of ARB and the variation of i/e ARG copy numbers were observed to reveal that the introduction of interfacial heating aggravated the cell lysis and accelerated the iARGs release, resulting in the inactivation of 7.27-log ARB and the elimination of 4.64-log iARGs and 2.23-log eARGs. Localized heating coupling with ·OH oxidation achieved a 143 % increase in iARGs removal compared to the conventional Fenton-like oxidation. The interfacial photothermal Fenton-like disinfection process exhibited remarkable material stability, robust disinfection performance, and effective suppression of horizontal gene transfer, underscoring its immense potential to mitigate the risk of ARG dissemination in reclaimed water systems.

Engineering Interfacial Molecular Interactions on Ag Hollow Fibre Gas Diffusion Electrodes for High Efficiency in CO2 Conversion to CO.

The electrochemical CO2 reduction reaction (CO2RR) occurs at the nanoscale interface of the electrode-electrolyte. Therefore, tailoring the interfacial properties in the interface microenvironment provides a powerful strategy to optimise the activity and selectivity of electrocatalysts towards the desired products. Here, the microenvironment at the electrode-electrolyte interface of the flow-through Ag-based hollow fibre gas diffusion electrode (Ag HFGDE) is modulated by introducing surfactant cetyltrimethylammonium bromide (CTAB) as the electrolyte additive. The porous hollow fibre configuration and gas penetration mode facilitate the CO2 mass transfer and the formation of the triple-phase interface. Through the ordered arrangement of hydrophobic long-alkyl chains, CTAB molecules at the electrode/electrolyte interface promoted CO2 penetration to active sites and repelled water to reduce the activity of competitive hydrogen evolution reaction (HER). By applying CTAB-containing catholyte, Ag HFGDE achieved a high CO Faradaic efficiency (FE) of over 95 % in a wide potential range and double the partial current density of CO. The enhancement of CO selectivity and suppression of hydrogen was attributed to the improvement of charge transfer and the CO2/H2O ratio enhancement. These findings highlight the importance of adjusting the local microenvironment to enhance the reaction kinetics and product selectivity in the electrochemical CO2 reduction reaction CO2RR.

Designing C9N10 Anchored Single Mo Atom as an Efficient Electrocatalyst for Nitrogen Fixation.

Electrochemical nitrogen reduction reaction (NRR) is a promising route for realizing green and sustainable ammonia synthesis under ambient conditions. However, one of the major challenges of currently available Single-atom catalysts (SACs) is poor catalytic activity and low catalytic selectivity, which is far away from the requirements of industrial applications. Herein, first-principle calculations within the density functional theory were performed to evaluate the feasibility of a single Mo atom anchored on a g-C9N10 monolayer (Mo@g-C9N10) as NRR electrocatalysts. The results demonstrated that the gas phase N2 molecule can be sufficiently activated on Mo@g-C9N10, and N2 reduction dominantly occurs on the active Mo atom via the preferred enzymatic mechanism, with a low limiting potential of -0.48 V. In addition, Mo@g-C9N10 possesses a good prohibition ability for the competitive hydrogen evolution reaction. More impressively, good electronic conductivity and high electron transport efficiency endow Mo SACs with excellent activity for electrocatalytic N2 reduction. This theoretical research not only accelerates the development of NRR electrocatalysts but also increases our insights into optimizing the catalytic performance of SACs.

Hydration‐effect Boosted Active Hydrogen Facilitates Neutral Ammonia Electrosynthesis from Nitrate Reduction

AbstractElectrocatalytic nitrate reduction to ammonia (NO3RR) in a neutral medium is a green and effective strategy for treating nitrate pollution meanwhile producing ammonia. However, the insufficient active hydrogen (H*) on the catalyst surface resulting from the sluggish Volmer step (H2O → H+ + OH−), and the competitive hydrogen evolution reaction (HER) caused by H* coupling severely restrict the enhancement of NO3RR activity. Herein, a hydration‐effect boosted H*‐rich strategy facilitating neutral ammonia electrosynthesis from nitrate reduction is proposed. The introduction of the hydration‐effect‐promoting element aluminum into the copper‐based catalyst forming CuAlO2, which adjusts the electron density distribution in the catalyst system, and the resulting hydration‐effect significantly promotes the H* generation in a neutral medium. Moreover, the rapid charge transfer at the CuO/CuAlO2 interface facilitates the reaction kinetics and the H* diffusion. More importantly, the introduction of Al weakens the overly strong adsorption of intermediates by CuO, thereby accelerating the hydrogenation process and suppressing HER. Thus, under neutral conditions, CuO/CuAlO2 reached a Faradaic efficiency and an ammonia yield as high as 97.81 ± 1.94% and 10.21 ± 0.64 mg h−1 cm−2 at −1.0 V versus RHE toward NO3RR.