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The electrocatalytic reduction of COx (including CO2 and CO) into value-added fuels and chemicals, particularly multi-carbon (C2+) alcohols, presents a significant opportunity to close the manmade carbon cycle and support sustainable energy systems. The catalytic performance of electrochemical reduction reactions of CO2 and CO (COxRR) is strongly correlated with the local microenvironments, the flow electrolyzer, and the catalysis approaches with flow electrolyzers, which contribute to the kinetic and thermodynamic landscape of the reaction, ultimately determining the efficiency and selectivity of the COxRR toward desired reduction products. However, controllable microenvironment construction, rationally designed flow electrolyzers, and matchable flow electrolyzers derived catalysis approaches chosen for improving COxRR-to-alcohol performance still face challenges. Building upon the foundation laid by previous research, this review article will provide an in-depth summary of the regulation of the catalytic reaction interface microenvironment, the design of flow electrolyzers, and the development of derived stepwise catalysis approaches with the flow electrolyzers, which provide a comprehensive and strategic approach to enhancing the COxRR process for alcohol production, offering valuable insights and innovative solutions that can significantly impact the field of COxRR conversion to alcohol and contribute to the development of more sustainable chemical production methods.
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In carbon dioxide electrochemical reduction (CO2ER), since isolated catalysts encounter challenges in meeting the demands of intricate processes for producing multi-carbon (C2+) products, tandem catalysis is emerging as a promising approach. Nevertheless, there remains an insufficient theoretical understanding of designing tandem catalysts. Herein, we utilized density functional theory (DFT) to screen 80 tandem catalysts for efficient CO2ER to C2 products systematically, which combines the advantages of nitrogen-doped carbon-supported transition metal single-atom catalysts (M-N-C) and copper clusters. Three crucial criteria were designed to select structures for generation and transfer of *CO and facilitate C-C coupling. The optimal Cu/RuN4-pl catalyst exhibited an excellent ethanol production capacity. Additionally, the relationship between CO adsorption strength and transfer energy barrier was established, and the influence of the electronic structure on its adsorption strength was studied. This provided a novel and well-considered solution and theoretical guidance for the design of rational composition and structurally superior tandem catalysts.
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Single Fe sites have been explored as promising catalysts for the CO2 reduction reaction to value-added CO. Herein, we introduce a novel molten salt synthesis strategy for developing axial nitrogen-coordinated Fe-N5 sites on ultrathin defect-rich carbon nanosheets, aiming to modulate the reaction pathway precisely. This distinctive architecture weakens the spin polarization at the Fe sites, promoting a dynamic equilibrium of activated intermediates and facilitating the balance between *COOH formation and *CO desorption at the active Fe site. Notably, the synthesized FeN5, supported on defect-rich in nitrogen-doped carbon (FeN5@DNC), exhibits superior performance in CO2RR, achieving a Faraday efficiency of 99% for CO production (-0.4 V vs. RHE) in an H-cell, and maintaining a Faraday efficiency of 98% at a current density of 270 mA cm-2 (-1.0 V vs. RHE) in the flow cell. Furthermore, the FeN5@DNC catalyst is assembled as a reversible Zn-CO2 battery with a cycle durability of 24 hours. In-situ IR spectroscopy and density functional theory (DFT) calculations reveal that the axial N coordination traction induces a transformation in the crystal field and local symmetry, therefore weakening the spin polarization of the central Fe atom and lowering the energy barrier for *CO desorption.
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Palladium (Pd) and gold (Au) are the most often used precious metals (PMs) in industrial catalysis and electronics. Green recycling of Pd and Au is crucial and difficult. Here, we report a peroxydisulfate (PDS)-based advanced oxidation process (AOPs) for selectively recovering Pd and Au from spent catalysts. The PDS/NaCl photochemical system achieves complete dissolution of Pd and Au. By introducing Fe(II), the PDS/FeCl2·4H2O solution functioned as Fenton-like system, enhancing the leaching efficiency without xenon (Xe) lamp irradiation. Electron paramagnetic resonance (EPR), 18O isotope tracing experiments, and density functional theory calculations revealed that the reactive oxidation species of SO4·-, ·OH, and Fe(IV)âO were responsible for the oxidative dissolution process. Lixiviant leaching and one-step electrodeposition recovered high-purity Pd and Au. Strong acids, poisonous cyanide, and volatile organic solvents were not used during the whole recovery, which enables an efficient and sustainable precious metal recovery approach and encourage AOP technology for secondary resource recycling.
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Metal-organic frameworks (MOFs) have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity, but the limited catalytic activity and stability has hampered their practical use in water splitting. Herein, we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs (donated as AE-CoNDA) to serve as efficient catalyst for water splitting. AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm-2 and a small Tafel slope of 62 mV dec-1 with excellent stability over 100 h. After integrated AE-CoNDA onto BiVO4, photocurrent density of 4.3 mA cm-2 is achieved at 1.23 V. Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p, which accounts for the fast kinetics and high activity. Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.
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Seawater electrolysis is a promising but challenging strategy to generate carbon-neutral hydrogen. A grand challenge for hydrogen evolution reaction (HER) from alkaline seawater electrolysis is the development of efficient and stable electrocatalysts to overcome the limitation of sluggish kinetics. Here, a 3D nanorod hybrid catalyst is reported, which comprises heterostructure MoO2@NiMoO4 supported Ru nanoparticles (Ru/ MoO2@NiMoO4) with a size of ≈5 nm. Benefitting from the effect of strongly coupled interaction, Ru/MoO2@NiMoO4 catalyst exhibits a remarkable alkaline seawater hydrogen evolution performance, featured by a low overpotential of 184 mV at a current density of 1.0 A cm-2, superior to commercial Pt/C (338 mV). Experimental observations demonstrate that the heterostructure MoO2@NiMoO4 as an electron-accepting support makes the electron transfer from the Ru nanoparticles to MoO2, and thereby implements the electron redistribution of Ru site. Mechanistic analysis elucidates that the electron redistribution of active Ru site enhances the ability of hydrogen desorption, thereby promoting alkaline seawater HER kinetics and finally leading to a satisfactory catalysis performance at ampere-level current density of alkaline seawater electrolysis.
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This study investigated the mechanisms of forming reactive species to degrade micropollutants through the activation of peroxymonosulfate (PMS) by phosphate, a prevalent ion in wastewater. Considering the density functional theory results, the formation of hydrogen bonds between phosphate and PMS molecules might be the crucial step in the overall reactions, which prefers producing â OH and reactive phosphate species (RPS, namely H2PO4â , HPO4â -, and PO4â 2-) to yielding SO4â -. Besides, in the phosphate (5 mM)/PMS system at pH = 8, HPO4â - was modeled to be the dominant radical with a steady-state concentration of 3.6 × 10-12 M, which was 666 and 773 times higher than those of â OH and SO4â -. The contributions of 1O2, â OH, SO4â -, and RPS to the micropollutant decomposition in phosphate/PMS were studied, and RPS were found to be selective for micropollutants with electron-donating moieties (such as phenolic and aniline groups). Additionally, the degradation pathways of bisphenol A, diclofenac, ibuprofen, and atrazine in phosphate/PMS were proposed according to the detected transformation products. Cytotoxicity analysis was carried out to evaluate the potential environmental impacts resulting from the degradation of micropollutants by phosphate/PMS. This study confirmed the significance of RPS for micropollutant degradation during PMS-based treatment in phosphate-rich scenarios.
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Atrazina , Fosfatos , Águas Residuárias , DiclofenacoRESUMO
Upgrading CO2 into multi-carbon (C2+) compounds through the CO2 reduction reaction (CO2 RR) offers a practical approach to mitigate atmospheric CO2 while simultaneously producing high value chemicals. The reaction pathways for C2+ production involve multi-step proton-coupled electron transfer (PCET) and C-C coupling processes. By increasing the surface coverage of adsorbed protons (*Had ) and *CO intermediates, the reaction kinetics of PCET and C-C coupling can be accelerated, thereby promoting C2+ production. However, *Had and *CO are competitively adsorbed intermediates on monocomponent catalysts, making it difficult to break the linear scaling relationship between the adsorption energies of the *Had /*CO intermediate. Recently, tandem catalysts consisting of multicomponents have been developed to improve the surface coverage of *Had or *CO by enhancing water dissociation or CO2 -to-CO production on auxiliary sites. In this context, we provide a comprehensive overview of the design principles of tandem catalysts based on reaction pathways for C2+ products. Moreover, the development of cascade CO2 RR catalytic systems that integrate CO2 RR with downstream catalysis has expanded the range of potential CO2 upgrading products. Therefore, we also discuss recent advancements in cascade CO2 RR catalytic systems, highlighting the challenges and perspectives in these systems.
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Electrochemical oxygen evolution reaction (OER) kinetics are heavily correlated with hybridization of the transition metal d-orbital and oxygen intermediate p-orbital, which dictates the barriers of intermediate adsorption/desorption on the active sites of catalysts. Herein, a strategy is developed involving strain engineering and coordination regulation to enhance the hybridization of Ni 3d and O 2p orbitals, and the as-synthesized Ni-2,6-naphthalenedicarboxylic acid metal-organic framework (DD-Ni-NDA) nanosheets deliver a low OER overpotential of 260 mV to reach 10 mA cm-2 . By integrating an alkaline anion exchange membrane electrolyzer and Pt/C electrode, 200 and 500 mA cm-2 current densities are reached with cell voltages of 1.6 and 2.1 V, respectively. When loaded on a BiVO4 photoanode, the nanosheet enables highly active solar-driven water oxygen. Structural characterizations together with theoretical calculations reveal that the spin state of the centre Ni atoms is regulated by the tensile strain and unsaturated coordination defects in DD-Ni-NDA, and such spin regulation facilitates spin-dependent charge transfer of the OER. Molecular orbital hybridization analysis reveals the mechanism of OH* and OOH* adsorption energy regulation by changes in the DD-Ni-NDA spin state, which provides a deeper understanding of the electronic structure design of catalysts for the OER.
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Electrosynthesis of H2 O2 has great potential for directly converting O2 into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical-level H2 O2 production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (FeSA -NS/C). The newly-developed FeSA -NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H2 O2 at a high current of 100â mA cm-2 with a record high H2 O2 selectivity of 90 %. An accumulated H2 O2 concentration of 5.8â wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally-designed catalytic active center with the atomic Fe site stabilized by three-coordinated nitrogen atoms and one-sulfur atom (Fe-N3 S-C). It was further found that the replacement of one N atom with S atom in the classical Fe-N4 -C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H2 O2 electrosynthesis.
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Electrochemical C-N coupling reactions based on abundant small molecules (such as CO2 and N2) have attracted increasing attention as a new "green synthetic strategy" for the synthesis of organonitrogen compounds, which have been widely used in organic synthesis, materials chemistry, and biochemistry. The traditional technology employed for the synthesis of organonitrogen compounds containing C-N bonds often requires the addition of metal reagents or oxidants under harsh conditions with high energy consumption and environmental concerns. By contrast, electrosynthesis avoids the use of other reducing agents or oxidants by utilizing "electrons", which are the cleanest "reagent" and can reduce the generation of by-products, consistent with the atomic economy and green chemistry. In this study, we present a comprehensive review on the electrosynthesis of high value-added organonitrogens from the abundant CO2 and nitrogenous small molecules (N2, NO, NO2-, NO3-, NH3, etc.) via the C-N coupling reaction. The associated fundamental concepts, theoretical models, emerging electrocatalysts, and value-added target products, together with the current challenges and future opportunities are discussed. This critical review will greatly increase the understanding of electrochemical C-N coupling reactions, and thus attract research interest in the fixation of carbon and nitrogen.
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Cu-based catalysts have been widely applied in electroreduction of carbon dioxide (CO2 ER) to produce multicarbon (C2+ ) feedstocks (e.g., C2 H4 ). However, the high energy barriers for CO2 activation on the Cu surface is a challenge for a high catalytic efficiency and product selectivity. Herein, we developed an in situ *CO generation and spillover strategy by engineering single Ni atoms on a pyridinic N-enriched carbon support with a sodalite (SOD) topology (Ni-SOD/NC) that acted as a donor to feed adjacent Cu nanoparticles (NPs) with *CO intermediate. As a result, a high C2 H4 selectivity of 62.5 % and an industrial-level current density of 160â mA cm-2 at a low potential of -0.72â V were achieved. Our studies revealed that the isolated NiN3 active sites with adjacent pyridinic N species facilitated the *CO desorption and the massive *CO intermediate released from Ni-SOD/NC then overflowed to Cu NPs surface to enrich the *CO coverage for improving the selectivity of CO2 ER to C2 H4 .
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In this work, a spinel oxide of MnFe2O4 was used as the dielectric barrier discharge (DBD) catalyst for the remediation of pyrene-contaminated soil. The performances were investigated through tuning voltage, frequency, catalyst dosage, and soil moisture. Under the optimal conditions, such as the voltage of 10.0 kV, the discharge frequency of 1.0 kHz, MnFe2O4 dosage of 0.3 g, air flow rate of 2.0 L min-1, soil humidity of 5.3%, and degradation efficiency of DBD/MnFe2O4 for pyrene could reach 79.26% after 10 min treatment, which was much higher than that of DBD for pyrene of 42.56%. The DBD/MnFe2O4 system also showed the high degradation efficiency of other pollutants including phenanthrene, p-nitrophenol, and p-nitrophenol in contaminated soil. The enhancing mechanism of the DBD/MnFe2O4 system was discussed.
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In the field of replacement of conventional dialysis treatment, searching superior materials for removal of protein-bound uremic toxins is a challenge on account of strong interactions between proteins and uremic toxins. Herein, we first adopted cationic metal-organic frameworks (MOFs), ZJU-X6 and ZJU-X7, as sorbents to decontaminate uremic toxins (p-cresyl sulfate and indoxyl sulfate). ZJU-X6 and ZJU-X7 exhibited innate advantage for sequestration of uremic toxins by utilizing a positive charge framework with exchangeable anions. Especially, ZJU-X6 showed a higher sorption capacity and faster sorption kinetics than those of most reported materials. Moreover, the cationic MOF materials could selectively remove uremic toxins even if in the presence of competitive chloride ions and proteins. Meanwhile, pair distribution function (PDF) and density functional theory (DFT) were employed to elucidate the sorption mechanism between uremic toxins and sorbents. This work suggests an attractive avenue for constructing new types of sorbents to eliminate uremic toxins for uremia treatment.
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Estruturas Metalorgânicas , Toxinas Biológicas , Humanos , Albumina Sérica Humana/metabolismo , Toxinas Urêmicas , Proteínas/metabolismo , Diálise Renal , CátionsRESUMO
Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm-2 with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni2-S1" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni2-S1" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity.
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Oxygen evolution reaction (OER) plays a key role in many renewable energy technologies such as water splitting and metal-air batteries. Metal-organic frameworks (MOFs) are appealing to design efficient OER electrocatalysts, however, their intrinsic poor conductivity strongly hinders the activity. Here, we show a strategy to boost the OER activity of poor-conductive MOFs by confining them between graphene multilayers. The resultant NiFe-MOF//G gives a record-low overpotential of 106 mV to reach 10 mA cm-2 and retains the activity over 150 h, which is in significant contrast to 399 mV of the pristine NiFe-MOF. We use X-ray absorption spectroscopy (XAS) and computations to demonstrate that the nanoconfinement from graphene multilayers not only forms highly reactive NiO6-FeO5 distorted octahedral species in MOF structure but also lowers limiting potential for water oxidation reaction. We also demonstrate that the strategy is applicable to other MOFs of different structures to largely enhance their electrocatalytic activities.
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Albeit reported substantial sorbents for elimination of TcO4-, the issue of secondary contamination caused by released counterions (such as NO3-) from the cationic metal-organic framework (MOF) has not come into the sufficient limelight for researchers. Herein, our efforts are dedicated to settle the matter through synthesis of NiCl2 based on the cationic MOF (ZJU-X4). Less harmful chlorides are used as exchangeable anions for replacing hazardous anions. Notably, ZJU-X4 exhibited fast sorption kinetics, high sorption capacity of 395 mg/g, decent selectivity, and excellent reusability in four recycles. The results of ion chromatography revealed that the released chloride ion was equal to sorption of target ions, and pair distribution functions were employed to analyze the changes in ZJU-X4 after sorption of ReO4-, clearly elucidating the anion-exchange mechanism. Furthermore, in the dynamic sorption experiments, ReO4- could be facilely and effectively removed and recovered, showing the value of practical applications. This work indicated that cationic MOF-based metal chloride salts would be a better choice for anionic sorbents.
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Two-dimensional metal-organic frameworks (MOFs) have served as favorable prototypes for electrocatalytic oxygen evolution reaction (OER). Despite promising catalytic activity, their OER reaction kinetics are still limited by the sluggish four-electron transfer process. Herein, we develop a ferrocene carboxylic acid (FcCA) partially substituted cobalt-terephthalic acid (CoBDC) catalyst with a bifunctional microreactor composed of two species of Co active sites and ligand FcCA (CoBDC FcCA). Benefiting from the ultrathin nanosheet structure, CoBDC FcCA catalyst exhibits an excellent OER performance with a low overpotential of 280 mV to reach 10 mA cm-2 and a small Tafel slope of 53 mV dec-1. Structure characterization together with theoretical calculations directly unravel the coordination for two species of Co active moieties with FcCA forming a microreactor of tensile strain, leading to a conversion of the Co spin from a high spin state (t2g5eg2) to an intermediate spin state (t2g6eg1) to regulate antibonding states of Co 3d and O 2p orbital. In situ spectroscopic measurements for mechanistic understanding reveal that this CoBDC FcCA catalyst possesses an optimal OH* adsorption energy for propitious formation of O-O bonds in the OOH* intermediate, thus effectively decreasing the thermodynamic Gibbs free energy of the rate-determining step (O* â OOH*) to accelerate reaction kinetics for the whole OER process. When loaded on an integrated BiVO4 photoanode as a cocatalyst, CoBDC FcCA enables highly active solar-driven oxygen production from water splitting.
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The electrochemical nitrogen reduction reaction (e-NRR) is envisaged as alternative technique to the Haber-Bosch process for NH3 synthesis. However, how to develop highly active e-NRR catalysts faces daunting challenges. Herein, a viable strategy to manipulate local spin state of isolated iron sites through S-coordinated doping (FeSA -NSC) is reported. Incorporation of S in the coordination of FeSA -NSC can induce the transition of spin-polarization configuration with the formation of a medium-spin-state of Fe (t2g 6 eg 1), which is beneficial for facilitating eg electrons to penetrate the antibonding π-orbital of nitrogen. As a consequence, a record-high current density up to 10 mA cm-2 can be achieved, together with a high NH3 selectivity of ≈10% in a flow cell reactor. Both experimental and theoretical analyses indicate that the monovalent Fe(I) atomic center in the FeSA -NSC after the S doping accelerates the N2 activation and protonation in the rate-determining step of *N2 to *NNH.
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Sulfide-driven denitrification (SD) process has been widely studied for treating wastewater containing sulfate and ammonia in recent years. But influence of high ammonia stress on the SD process and microbial community remained unclear. In this work, a series of tests were conducted to investigate effects of different ammonia stress (200-3000 mg-total ammonia nitrogen (TAN)/L) on denitrification efficiency, byproduct accumulation and microbial community of the SD process. According to our results, the SD process was severely inhibited, and 32.67 ± 5.15 mg/L NO2--N was accumulated when ammonia stress reached 3000 mg TAN/L. But the inhibited SD process could recover in about 40 days when ammonia stress was decreased to 200 mg TAN/L. After analyzing the microbial community, Thiobacillus sp. (Thiobacillus sp. 65-29, Thiobacillus sp. SCN 64-317, Thiobacillus sp. 63-78 and Thiobacillus denitrificans) was confirmed as dominant bacteria responsible for the SD process. Further, expression of narG, napA, nirK and nirS were inhibited under high ammonia stress, thus making the SD process stuck in NO3- and NO2- reduction step. This study reveals the inhibitory effects of high ammonia stress on the SD process and its possible underlying mechanism with discussion in gene level.