Oxidation Of Formaldehyde Research Articles

Mesopore Catalytic Activated‐Carbon to Reduce Harmful Gases Indoors: Adsorption, Catalytic Oxidation, and Prediction Mechanism

ABSTRACTModification of local bamboo‐based catalytic activated carbon with metallic Ag can produce mesopore and micropore types, with a mesopore content of 86%. One of the best ways to reduce formaldehyde concentrations is through catalytic adsorption. In combination with Ag nanoparticle catalyst, formaldehyde adsorption capacity is improved. Adsorption and oxidation reaction experiments are performed in a fixed bed column (di = 10 mm, length = 90 mm). The increase in formaldehyde adsorption associated with the reaction rate of formaldehyde oxidation by metallic Ag is 51 g/mmol. The oxidation reaction of Ag nanoparticles is a bimolecular reaction based on the Langmuir–Hinshelwood mechanism. Formaldehyde can be reduced by 59% and 41% through the role of adsorption and support of catalytic oxidation, respectively. Additionally, harmless gases such as CO2 and H2O are produced within the column.

Interfacial adsorption and catalysis of single-atom Pt-loaded ZrO2 surfaces for enhancing formaldehyde oxidation

The emerging transition metal single-atom catalysts (SACs) are expected to have high activity for converting detrimental formaldehyde (HCHO) under mild conditions. Currently, the exploitation of novel SACs with designed or modified support surfaces remains largely imperative. Herein, we used density functional theory to explore the catalytic performance for HCHO oxidation on various single-atom Pt-loaded ZrO2 surfaces, in which oxygen vacancy and lattice hydroxyl group were included on the surfaces. The surface modifications could enhance the co-adsorption of HCHO and O2 molecules and provide more active sites due to interfacial electron redistribution. The transition state search approach was applied to investigate the oxidation pathways on various ZrO2-supported SAC surfaces, wherein distinct dehydrogenation mechanisms and intermediates were clarified. The oxygen vacancy defects and hydroxyl groups can enhance the catalytic activity for HCHO oxidation by providing active receptor sites for the H-transfer and facilitating the CH bond breakage. Microkinetic modeling was further used to characterize the reaction rates and kinetics behavior of HCHO oxidation on the SAC surfaces. Our simulation demonstrates the excellent catalytic performance of the modified ZrO2-supported SAC in the HCHO oxidation. Meanwhile, the mechanism is also an important implication for the synthesis and design of novel SACs.

Room temperature thermocatalytic removal of formaldehyde in air using a copper manganite spinel-supported palladium catalyst with ultralow noble metal content

The room temperature (RT)-catalytic oxidation of gaseous formaldehyde (FA) in the dark is regarded as one of the most viable technical options for its removal from indoor air. Herein, the copper manganite spinel (CuMn2O4) supported palladium (Pd) catalysts are firstly synthesized for the thermocatalytic oxidation of FA in air. In particular, 0.05% Pd-CuMn2O4-R (‘R’ denotes high-temperature reduction pre-treatment using hydrogen) achieves 100% conversion (XFA) of 50 ppm FA at RT (gas hourly space velocity of 4342 h−1). The performance of 0.05% Pd-CuMn2O4-R against FA, if assessed in terms of the reaction kinetic rate (r at 10% XFA), is estimated as 3.01E−02 mmol g−1h−1. The lowering of XFA with the increases in FA concentration, flow rate, and relative humidity indicates the detrimental effects of such variables on the catalytic activity. FA oxidation kinetics predominantly follows the Mars van Krevelen mechanism. In-situ diffuse reflectance infrared Fourier transform spectroscopy shows that FA oxidation proceeds through multiple reaction intermediates (e.g., dioxymethylene and formate). The density functional theory simulations indicate that the catalytic oxidation efficacy of FA over CuMn2O4 increases by the synergy between Pd loading and surface reduction. The present study represents the first report on the synthesis of CuMn2O4-supported Pd catalysts and their application for the RT oxidative removal of FA in air under dark conditions. The findings of the present work offer valuable insights into the construction of efficient and cost-effective catalysts with ultra-low noble metal content for the RT oxidative removal of VOCs in indoor environment.

Accelerating the production of formate radicals for nitrate purification via a redox-regulated photocatalysis route

The treatment of nitrate (NO3−) pollutants is crucial for human health in the context of environmental pollution. Synergistic photocatalytic redox technology is feasible for reducing low-concentrated NO3− to achieve environmental purification. As combined redox reactions proceed in one photocatalysis system, incorporating suitable oxidative reactions is one potential strategy to enhance photocatalytic NO3− reduction efficiency. Herein, almost 100 % removal efficiency of NO3− and superior N2 selectivity of 93.99±0.45 % is achieved through the precise matching of synergistic oxidative half-reactions. The crucial role of active radicals is revealed. Specifically, the conversion efficiency of NO3− is determined by the cooperation of formate radicals (•CO2−), which are generated from the selective oxidation of formaldehyde, acetaldehyde or glyoxal. Among them, the optimum yield of •CO2− radicals are reached from the formaldehyde oxidative reaction. It is clarified that this research will contribute to a deep understanding of the removal and purification of NO3− in wastewater.

The practical utility of nitrogen doped TiO2 as a photocatalyst for the oxidative removal of gaseous formaldehyde

This study reports the development of nitrogen-doped TiO2 (N–TiO2: N/Ti molar ratio = 1) photocatalyst with the enhanced photoelectronic properties for the phtocatalytic oxidation (PCO) of formaldehyde (FA). The N–TiO2 photocatalyst is coated with ceramic beads and placed in a packed-bed tube reactor to examine the PCO-based mineralization of FA vapor (100 - 500 ppm) under ultraviolet (UV)-A illumination (32 W light source) with the control of flow rate (100–500 mL min−1), O2 (0–21%), and relative humidity (RH: 0–100%). Accordingly, the N-TiO2 in dry conditions showcases 100% degradation of 100 ppm FA with high stability over 5 reuse cycles (compared to the P25 (75.9%) and bare TiO2 (69.2%)) at a flow rate of 100 mL min−1 and a 21 % O2 level (quantum yield = 1.72.E−02 molecules photon−1 and space-time yield = 3.44.E−03 molecules photon−1 mg−1). The superior performance of N–TiO2 may reflect the combination of N/O atoms in the crystal structure to enhance the photo-redox reactivities with the heightened valence band enegry and prolonged lifespan of charge carrier (1.34 ns) relative to 1.04 ns of P25 and 1 ns of pure (anatase) TiO2. The PCO efficiency of N–TiO2 increases by around 1.6 times in slightly humid conditions (74.6%: RH 20%) compared to dry conditions (47%: RH 0%) while the absence of oxygen (at 0% O2) reduces it significantly down to 13.6%. In situ diffuse reflectance infrared Fourier transform spectroscopy and electron paramagnetic resonance studies confirm the critical role of O2 and H2O vapor on the enhanced FA mineralization rate (CO2 yield = 91 %) through the generation of •O2-/•OH oxidative radicals. This study offers deep insights into the practical utility of N–TiO2 for the photocatalytic mineralization of aldehyde VOCs.

Fe-doped BN monolayer: A single-atom catalyst for efficient formaldehyde oxidation

Formaldehyde (HCHO) is a ubiquitous air pollutant, and the prolonged inhalation poses a serious threat to human health, thus it is imperative to develop HCHO oxidation catalysts with high activity. FeNx-based catalysts have shown brilliant catalytic performance due to their unique electronic structures. In this work, the active FeN3 site is designed by doping Fe atom at the B-vacancy in BN monolayer without introducing additional N atoms. Our first principles calculation results show that the Fe atom has good dispersibility, dynamical stability and thermal stability on the BN monolayer. Two oxidation mechanisms (Langmuir-Hinshelwood and Eley-Rideal) of HCHO on Fe-doped BN monolayer are investigated to explore the possible reaction pathways. The dissociation of O2 molecule is identified as the rate-limiting step, and the lowest energy barrier is 0.99 eV. Moreover, the excellent desorption behaviors of the produced CO2 and H2O molecules on substrate (small desorption energy of 0.20 and 0.75 eV, and short desorption time of 2.39 × 10−9 and 4.64 s) enable this catalyst to maintain high activity during the reaction cycle. Our results suggest the feasibility of Fe-doped BN monolayer for the catalytic oxidation of HCHO and broaden the application of BN-based single-atom catalysts.

Gene-centered metagenome analysis of Vulcano Island soil (Aeolian archipelago, Italy) reveals diverse microbial key players in methane, hydrogen and sulfur cycles

The Aeolian archipelago is known worldwide for its volcanic activity and hydrothermal emissions, of mainly carbon dioxide and hydrogen sulfide. Hydrogen, methane, and carbon monoxide are minor components of these emissions which together can feed large quantities of bacteria and archaea that do contribute to the removal of these notorious greenhouse gases. Here we analyzed the metagenome of samples taken from the Levante bay on Vulcano Island, Italy. Using a gene-centric approach, the hydrothermal vent community appeared to be dominated by Proteobacteria, and Sulfurimonas was the most abundant genus. Metabolic reconstructions highlight a prominent role of formaldehyde oxidation and the reverse TCA cycle in carbon fixation. [NiFe]-hydrogenases seemed to constitute the preferred strategy to oxidize H2, indicating that besides H2S, H2 could be an essential electron donor in this system. Moreover, the sulfur cycle analysis showed a high abundance and diversity of sulfate reduction genes underpinning the H2S production. This study covers the diversity and metabolic potential of the microbial soil community in Levante bay and adds to our understanding of the biogeochemistry of volcanic ecosystems.

The performance and mechanism of HCHO oxidation on Pt/Al2O3 catalysts: The effect of alumina crystalline phase and surface hydroxyls

The performance and mechanism of formaldehyde (HCHO) oxidation on Pt/γ-Al2O3, Pt/θ-Al2O3 and Pt/α-Al2O3 catalysts were investigated, focusing on the impact of OH species, H2O participation and the difference in Pt sites. Characterization revealed that the catalytic performance of Pt/Al2O3 catalysts is predominantly influenced by surface OH rather than other factors. Through CO-TPR and 2D COS analysis, the existence and functions of Pt-OH and Al-OH were distinguished, along with the active and spectator formate species derived therefrom. The introduction of H2O promotes the regeneration of Pt-OH, as well as the migration of intermediate species, which explains the enhancement on catalytic performance under relative humidity. Meanwhile, the proportion of partially oxidized Pt/Pt-terrace/Pt-step would impact the ability of Pt-OH replenishment, further influencing the catalytic activity. These findings highlight the critical role of surface OH species and provide a deeper insight into understanding the OH-effected mechanism in HCHO oxidation.

Deactivation of layered MnO2 catalyst during room temperature formaldehyde degradation and its thermal regeneration mechanism

Layered δ-MnO2 prepared by a one-step redox method was shown to be deactivated during oxidation of formaldehyde at room temperature. Recovery of the formaldehyde degradation activity was investigated after thermal regeneration at different temperatures. XRD, SEM, TEM, H2-TPR, XPS, TGA and DRIFTS characterization were used to analyze the physical properties of fresh, deactivated and thermally regenerated catalysts. The results showed that deactivation of catalyst was caused by less oxygen vacancies due to increased Mn4+ content during formaldehyde degradation and formation of formate blocking active sites. Thermal regeneration helped to decompose formate at the catalyst surface, restoring some of the active sites. Interplanar spacing of MnO2 became wider and the number of Mn3+ on exposed crystal faces increased. More oxygen vacancies were formed. The activity of deactivated catalyst was restored. Formaldehyde degradation rate of catalyst regenerated at 200 °C remained above 80 % after 6 h, demonstrating the possibility of waste layered catalyst recycling.

Sepiolite-Supported Manganese Oxide as an Efficient Catalyst for Formaldehyde Oxidation: Performance and Mechanism.

The current study involved the preparation of a number of MnOx/Sep catalysts using the impregnation (MnOx/Sep-I), hydrothermal (MnOx/Sep-H), and precipitation (MnOx/Sep-P) methods. The MnOx/Sep catalysts that were produced were examined for their ability to catalytically oxidize formaldehyde (HCHO). Through the use of several technologies, including N2 adsorption-desorption, XRD, FTIR, TEM, H2-TPR, O2-TPD, CO2-TPD, and XPS, the function of MnOx in HCHO elimination was examined. The MnOx/Sep-H combination was shown to have superior catalytic activities, outstanding cycle stability, and long-term activity. It was also able to perform complete HCHO conversion at 85 °C with a high GHSV of 6000 mL/(g·h) and 50% humidity. Large specific surface area and pore size, a widely dispersed active component, a high percentage of Mn3+ species, and lattice oxygen concentration all suggested a potential reaction route for HCHO oxidation. This research produced a low-cost, highly effective catalyst for HCHO purification in indoor or industrial air environments.

Double-Cabin Galvanic Cell-Synthesizing Nanoporous, Flower-like, Pb-Containing Pd-Au Nanoparticles for Nonenzymatic Formaldehyde Sensor.

In this work, a novel formaldehyde sensor was constructed based on nanoporous, flower-like, Pb-containing Pd-Au nanoparticles deposited on the cathode in a double-cabin galvanic cell (DCGC) with a Cu plate as the anode, a multiwalled carbon nanotube-modified glassy carbon electrode as the cathode, a 0.1 M HClO4 aqueous solution as the anolyte, and a 3.0 mM PdCl2 + 1.0 mM HAuCl4 + 5.0 mM Pb(ClO4)2 + 0.1 M HClO4 aqueous solution as the catholyte, respectively. Electrochemical studies reveal that the stripping of bulk Cu can induce underpotential deposition (UPD) of Pb during the galvanic replacement reaction (GRR) process, which affects the composition and morphology of Pb-containing Pd-Au nanoparticles. The electrocatalytic activity of Pb-containing nanoparticles toward formaldehyde oxidation was examined in an alkaline solution, and the experimental results showed that formaldehyde mainly caused direct oxidation on the surface of Pb-containing Pd-Au nanoparticles while inhibiting the formation of CO poison to a large degree. The proposed formaldehyde sensor exhibits a linear amperometric response to formaldehyde concentrations from 0.01 mM to 5.0 mM, with a sensitivity of 666 μA mM-1 cm-2, a limit of detection (LOD) of 0.89 μM at triple signal-to-noise, rapid response, high anti-interference ability, and good repeatability.

Synergistic doping and de-doping of Co3O4 catalyst for effortless formaldehyde oxidation

The pursuit of high-performance non-precious metal catalysts for Volatile Organic Compounds (VOCs) abatement is paramount in meeting stringent environmental regulations. In this study, we present a groundbreaking approach by crafting a highly defective Co3O4 catalyst through a strategic process involving Mg doping and subsequent partial de-doping. The catalyst exhibited an exceptional activity in the oxidation of formaldehyde (HCHO), achieving a remarkable conversion rate of 2.92 μmol·m−2·h−1, which is 3.1 times that of the pristine Co3O4 at 100 °C and an HCHO space velocity of 75,000 mL·g−1·h−1. Our methodology involves a dual-action process of doping and de-doping, orchestrating the introduction of significant structural and surface defects. These include surface cracks, lattice distortions, cationic vacancies, oxygen vacancies, lower metal coordination, and more. This orchestrated creation of defects serves to amplify the generation of active oxygen sites, thereby enhancing the intrinsic oxidative ability of the catalyst. The net result is a lowered activation energy barrier for HCHO, further contributing to the catalyst performance enhancement. This study not only establishes a new benchmark for Co3O4 catalysis but also provides insightful paradigms for the role of defects engineering in promoting non-noble metal-catalyzed volatile organic compounds oxidation.

Metal Doped Unconventional Phase IrNi Nanobranches: Tunable Electrochemical Nitrate Reduction Performance and Pollutants Upcycling.

Electrochemical nitrate reduction (NO3RR) provides a new option to abate nitrate contamination with a low carbon footprint. Restricted by competitive hydrogen evolution, achieving satisfied nitrate reduction performance in neutral media is still a challenge, especially for the regulation of this multielectron multiproton reaction. Herein, facile element doping is adopted to tune the catalytic behavior of IrNi alloy nanobranches with an unconventional hexagonal close-packed (hcp) phase toward NO3RR. In particular, the obtained hcp IrNiCu nanobranches favor the ammonia production and suppress byproduct formation in a neutral electrolyte indicated by in situ differential electrochemical mass spectrometry, with a high Faradaic efficiency (FE) of 85.6% and a large yield rate of 1253 μg cm-2 h-1 at -0.4 and -0.6 V (vs reversible hydrogen electrode (RHE)), respectively. In contrast, the resultant hcp IrNiCo nanobranches promote the formation of nitrite, with a peak FE of 33.1% at -0.1 V (vs RHE). Furthermore, a hybrid electrolysis cell consisting of NO3RR and formaldehyde oxidation is constructed, which are both catalyzed by hcp IrNiCu nanobranches. This electrolyzer exhibits lower overpotential and holds the potential to treat polluted air and wastewater simultaneously, shedding light on green chemical production based on contaminate degradation.

High-Throughput Screening Strategy for Electrocatalysts for Selective Catalytic Oxidation of Formaldehyde to Formic Acid.

Electrocatalytic oxidation of formaldehyde (FOR) is an effective way to prevent the damage caused by formaldehyde and produce high-value products. A screening strategy of a single-layer MnO2-supported transition metal catalyst for the selective oxidation of formaldehyde to formic acid was designed by high-throughput density functional calculation. N-MnO2@Cu and MnO2@Cu are predicted to be potential FOR electrocatalysts with potential-limiting steps (PDS) of 0.008 and -0.009 eV, respectively. Electronic structure analysis of single-atom catalysts (SACs) shows that single-layer MnO2 can regulate the spin density of loaded transition metal and thus regulate the adsorption of HCHO (Ead), and Ead is volcanically distributed with the magnetic moment descriptor -|mM - mH|. In addition, the formula quantifies Ead and |mM - mH| to construct a volcano-type descriptor α describing the PDS [ΔG(*CHO)]. Other electronic and structural properties of SACs and α are used as input features for the GBR method to construct machine learning models predicting the PDS (R2 = 0.97). This study hopes to provide some insights into FOR electrocatalysts.

Nonstatistical Unimolecular Decay of the CH2OO Criegee Intermediate in the Tunneling Regime.

Unimolecular decay of the formaldehyde oxide (CH2OO) Criegee intermediate proceeds via a 1,3 ring-closure pathway to dioxirane and subsequent rearrangement and/or dissociation to many products including hydroxyl (OH) radicals that are detected. Vibrational activation of jet-cooled CH2OO with two quanta of CH stretch (17-18 kcal mol-1) leads to unimolecular decay at an energy significantly below the transition state barrier of 19.46 ± 0.25 kcal mol-1, refined utilizing a high-level electronic structure method HEAT-345(Q)Λ. The observed unimolecular decay rate of 1.6 ± 0.4 × 106 s-1 is 2 orders of magnitude slower than that predicted by statistical unimolecular reaction theory using several different models for quantum mechanical tunneling. The nonstatistical behavior originates from excitation of a CH stretch vibration that is orthogonal to the heavy atom motions along the reaction coordinate and slow intramolecular vibrational energy redistribution due to the sparse density of states.

Self-heating photothermal synergistic catalytic decomposition of carcinogenic formaldehyde by α-MnO2 at ambient temperature: Functional roles of surface acidic-basic sites

Formaldehyde is a major pollutant in indoor atmosphere, and the realization of complete mineralization of formaldehyde at room temperature is of great significance and practical demand for improving indoor air quality. Surface acidic-basic sites, as one of the important surface properties that have significant influence on catalytic oxidation of formaldehyde, revealing their functions is beneficial for the development of efficient formaldehyde decomposition materials. Herein, the α-MnO2 acidic-basic sites were regulated and its effects on self-heating photothermal catalytic oxidation of formaldehyde were further contrastive investigated. The acidic-basic sites showed distinct functions: the basic sites exhibited a significant promotion on formaldehyde oxidation; While the acidic sites greatly inhibited the reactivity. Particularly, the basicity enhanced α-MnO2 could reach the 100% conversion of formaldehyde at ambient temperature. Furthermore, the self-heating photothermal mechanism was consonant with the thermal-assisted photocatalysis mechanism, rather than traditional photo-drive thermal catalysis mechanism. The strength of basic sites significantly increased the content of surface hydroxyl groups, and the electron-rich basic sites were favorable for the activation of oxygen, thereby generating more reactive oxygen species for the decomposition of formaldehyde. Moreover, in-situ DRIFTS reveals that the enhancement of basic sites can accelerate the rate oxidation of HCHO to generate formates and carbonates. This work clarified the influence of surface acid-base properties on formaldehyde photothermal decomposition.

Thermocatalytic oxidation potential of cobalt(II,III) oxide against gaseous formaldehyde in relation to hydrothermal synthesis temperature

The catalytic activity of various transition metal oxides has been reported to be tuned by controlling their synthesis conditions. In this perspective, the thermocatalytic oxidation performance of cobalt(II,III) oxides (Co3O4) against formaldehyde (FA) is studied in relation to the temperature selected for their hydrothermal synthesis (e.g., 30 (as room temperature (RT)), 60, 120, and 250℃) with the corresponding sample codes as Co3O4-RT, Co3O4-60, Co3O4-120, and Co3O4-250, respectively. The best performing Co3O4-RT records the lowest T90 (temperature required to obtain 90 % conversion) for 50 ppm FA at 72 °C when operated at 0 % relative humidity (RH), 30 mg (catalyst mass: mcat), and 100,000 mL g-1h−1 (weight hourly space velocity). The performance of Co3O4-RT, if assessed in terms of reaction kinetic rate (r) at XFA = 10 %, is 2.02E-02 mmol g-1h−1. According to X-ray photoelectron spectroscopy and temperature programmed characterization analysis, the catalytic activities of Co3O4-RT improve greatly through the synergistic combination of diverse factors (e.g., high Co3+ content, abundant oxygen vacancies (OVs) and surface adsorbed oxygen (Oβ) species, and good surface lattice oxygen (Oα) mobility). The analysis of in-situ diffuse reflectance infrared Fourier transform spectroscopy indicates that the FA should be oxidized into water (H2O) and carbon dioxide (CO2) via dioxymethylene (DOM) and formate (HCOO–) as reaction intermediates. The density functional theory simulations suggest the (111) surface of Co3O4 to be catalytically active against FA. The output of this research is expected to help establish effective strategies for designing high-performance transition metal oxide catalysts for the catalytic oxidation of FA.

Lattice-confined Ag over MnCoLDH accelerated catalytic oxidation of formaldehyde at ambient temperature: The novel pathway with different oxygen species

Catalytic oxidation of formaldehyde (HCHO) at ambient temperature represents a cost-effective and efficient strategy for indoor HCHO removal. Although precious metal-based catalysts have been considered practical for oxidizing gaseous HCHO indoors, the limited activity of Ag-based catalysts can be attributed to their typical +1 and 0 valence states, as well as their single electron transport pathway. This characteristic impedes the reestablishment of the low state during oxygen activation, thereby resulting in catalyst deactivation. The present study successfully incorporated Ag atoms into manganese-cobalt layered double hydroxide (MnCoLDH) through doping, resulting in the development of a catalyst that exhibited complete formaldehyde oxidation activity at 30 °C. Lattice-confined Ag enables continuous activation of oxygen, while LDH facilitates the sustained provision of surface hydroxyl groups. The roles and mechanisms of surface hydroxyl groups, adsorbed oxygen, and lattice oxygen in the oxidation of formaldehyde were investigated using in-situ DRIFTS. By comparing Ag with the impregnation method, the confinement of Ag within the lattice enables continuous activation of oxygen. This study presents a viable strategy for designing efficient catalysts for volatile organic compounds (VOCs) removal by utilizing active lattice oxygen species.

Efficient catalytic oxidation of formaldehyde by defective g–C3N4–anchored single-atom Pt: A DFT study

Indoor volatile formaldehyde is a serious health hazard. The development of low-temperature and efficient nonhomogeneous oxidation catalysts is crucial for protecting human health and the environment but is also quite challenging. Single-atom catalysts (SACs) with active centers and coordination environments that are precisely tunable at the atomic level exhibit excellent catalytic activity in many catalytic fields. Among two-dimensional materials, the nonmagnetic monolayer material g-C3N4 may be a good platform for loading single atoms. In this study, the effect of nitrogen defect formation on the charge distribution of g-C3N4 is discussed in detail using density functional theory (DFT) calculations. The effect of nitrogen defects on the activated molecular oxygen of Pt/C3N4 was systematically revealed by DFT calculations in combination with molecular orbital theory. Two typical reaction mechanisms for the catalytic oxidation of formaldehyde were proposed based on the Eley-Rideal (E-R) mechanism. Pt/C3N4–V3N was more advantageous for path 1, as determined by the activation energy barrier of the rate-determining step and product desorption. Finally, the active centers and chemical structures of Pt/C3N4 and Pt/C3N4–V3N were verified to have good stability at 375 K by determination of the migration energy barriers and ab initio molecular dynamics simulations. Therefore, the formation of N defects can effectively anchor single-atom Pt and provide additional active sites, which in turn activate molecular oxygen to efficiently catalyze the oxidation of formaldehyde. This study provides a better understanding of the mechanism of formaldehyde oxidation by single-atom Pt catalysts and a new idea for the development of Pt as well as other metal-based single-atom oxidation catalysts.

Chlorine-oxidation-free dual hydrogen production by seawater electrolysis coupling formaldehyde oxidation

The main challenges hindering the practical application of seawater electrolysis are the substantial energy input for sluggish oxygen evolution reaction (OER) and anode corrosion by chlorine oxidation reaction (COR). Here we report a simple but reliable strategy of coupling seawater electrolysis with formaldehyde oxidation reaction (FOR) to achieve energy-saving and COR-free dual hydrogen production. For the anode FOR, the onset potential is cut to near -0.2 V vs. the reversible hydrogen electrode (RHE) much lower than the theoretical potential of OER (1.23 V vs. RHE), and the Faradaic efficiencies of both hydrogen and high-value formate products achieve nearly 100 %. In a two-electrode electrolyzer at 100 mA cm−2, the cell voltage of our integrated system is 1.75 V lower than that of the conventional seawater electrolysis, leading to a 66 % reduction in electricity consumption. Moreover, benefiting from the ultra-low reaction potential, the harmful COR is fundamentally avoided. This work opens up a new way to efficiently and stably convert sea resources into hydrogen fuel while also achieving chemical upgrades.