Oxidation Of Formaldehyde Research Articles

Machine-Learning-Assisted Descriptors Identification for Indoor Formaldehyde Oxidation Catalysts.

The development of highly efficient catalysts for formaldehyde (HCHO) oxidation is of significant interest for the improvement of indoor air quality. Up to 400 works relating to the catalytic oxidation of HCHO have been published to date; however, their analysis for collective inference through conventional literature search is still a challenging task. A machine learning (ML) framework was presented to predict catalyst performance from experimental descriptors based on an HCHO oxidation catalysts database. MnOx, CeO2, Co3O4, TiO2, FeOx, ZrO2, Al2O3, SiO2, and carbon-based catalysts with different promoters were compiled from the literature. Notably, 20 descriptors including reaction catalyst composition, reaction conditions, and catalyst physical properties were collected for data mining (2263 data points). Furthermore, the eXtreme Gradient Boosting algorithm was employed, which successfully predicted the conversion efficiency of HCHO with an R-square value of 0.81. Shapley additive analysis suggested Pt/MnO2 and Ag/Ce-Co3O4 exhibited excellent catalytic performance of HCHO oxidation based on the analysis of the entire database. Validated by experimental tests and theoretical simulations, the key descriptor identified by ML, i.e., the first promoter, was further described as metal-support interactions. This study highlights ML as a useful tool for database establishment and the catalyst rational design strategy based on the importance of analysis between experimental descriptors and the performance of complex catalytic systems.

Density functional theory-based screening of Ti4C3O2-loaded single atoms for efficient selective catalytic oxidation of formaldehyde

Indoor formaldehyde (HCHO) pollution poses a major risk to human health. Low-temperature catalytic oxidation is an effective method for HCHO removal. The high activity and selectivity of single atomic catalysts provide a possibility for the development of efficient non-precious metal catalysts. In this study, the most stable single-atom catalyst Ti-Ti4C3O2 was screened by density functional theory among many single atomic catalysts with two-dimensional (2D) monolayer Ti4C3O2 as the support. The computational results show that Ti-Ti4C3O2 is highly selective to HCHO and O2 in complex environments. The HCHO oxidation reaction pathways are proposed based on the Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms. According to the reaction energy and energy span models, the E-R mechanism has a lower maximum energy barrier and higher catalytic efficiency than the L-H mechanism. In addition, the stability of the Ti-Ti4C3O2 structure and active center was verified by diffusion energy barrier and ab initio molecular dynamics simulations. The above results indicate that Ti-Ti4C3O2 is a promising non-precious metal catalyst. The present study provides detailed theoretical insights into the catalytic oxidation of HCHO by Ti-Ti4C3O2, as well as an idea for the development of efficient non-precious metal catalysts based on 2D materials.

Promoting effect of potassium over Pd/SiO2 catalyst for ambient formaldehyde oxidation

Highly dispersed noble metals are acknowledged for its pivotal role in influencing the efficiency of catalysts during the HCHO oxidation process. Interestingly, in this work, an innovative approach was employed to augmenting the stabilization of noble metals on irreducible carriers supported noble metal catalyst (Pd/SiO2) by adding alkali metal potassium (K). A formidable promotion effect was observed when the K doping to Pd/SiO2 catalysts. It achieves a conversion rate of 93% for 270 ppmV of HCHO to harmless CO2 and H2O at a weight hourly space velocity (WHSV) of 300,000 mL/(g·hr) at 25°C. Multiple characterization results illustrated that a strong interaction between added K and Pd species was formed after K addition, which not only stabilized Pd species on the carrier surface but also markedly enhanced its dispersal on the SiO2 carrier. The increasing Pd dispersion induced more oxygen vacancies on the surfaces of the Pd/SiO2 catalysts. The formation of these oxygen vacancies can be attributed to the phenomenon of hydrogen spillover, which also contributed to elevating the electron density on the Pd sites. Meanwhile, the oxygen vacancies favored the O2 activation to form more reactive oxygen species participating in the HCHO oxidation reaction, thus improving the performance of Pd/SiO2 catalysts displayed for HCHO oxidation. This study provides a simple strategy to design high-performance irreducible carriers supported noble metal catalysts for HCHO catalytic oxidation.

L-arginine-etched nickel-silver electrocatalyst for low-potential hydrogen evolution

The oxidation of formaldehyde at low potentials to achieve anodic hydrogen production is a crucial focus of current research. Copper-based alloys are prominent electrocatalysts in these reactions but face long-term stability challenges and are susceptible to CO intermediate poisoning. A novel approach that utilizes L-arginine in the surface modification of nickel foam substrates has been developed, enabling the highly dispersed deposition of silver catalysts on the substrates as sub-nanometer particles. This modified electrocatalyst allows formaldehyde oxidation and water electrolysis at a minimal potential of 0.32 VRHE and bipolar hydrogen production with near 100% Faradaic efficiency. This surface modification of substrate material provides a new approach to the design of electrodes.

Photocatalytic oxidation of formaldehyde under visible light using BiVO4-TiO2 synthesized via ultrasonic blending.

Formaldehyde (HCHO) is one of the primary indoor air pollutants, and efficiently eliminating it, especially at low concentrations, remains challenging. In this study, BiVO4-TiO2 catalyst was developed using ultrasonic blending technology for the photocatalytic oxidation of low-level indoor HCHO. The crystal structure, surface morphology, element distribution, and active oxidation species of the catalyst were examined using XRD, SEM, TEM, UV-Vis, EDS, and ESR techniques. Our results demonstrated that the BiVO4-TiO2 catalyst, prepared by ultrasonic blending, exhibited good oxidation performance and stability. The HCHO concentration reduced from 1.050 to 0.030mg/m3 within 48h, achieving a removal rate of 97.1%. The synergy between BiVO4 and TiO2 enhanced the efficiency of separating photogenerated carriers and minimized the likelihood of recombination between photogenerated electrons and holes. Additionally, this synergy significantly enhanced the presence of hydroxyl radicals (·OH) on the catalyst, resulting in an oxidation performance superior to that of either BiVO4 or TiO2. Our research offers valuable insights for the development of new photocatalysts to address HCHO pollution.

The practical utility of ternary nickel-cobalt-manganese oxide-supported platinum catalysts for room-temperature oxidative removal of formaldehyde from the air

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel–cobalt-manganese oxide–supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h−1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir–Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO–, and CO32–. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

The effects of metal-oxide content in MnO2-activated carbon composites on reactive adsorption and catalytic oxidation of formaldehyde and toluene in air

The deterioration in air quality caused by volatile organic compounds (VOCs) has become an important environmental issue. Here, activated carbon (AC) composites with manganese oxide (MnO2: 1 % to 50 %) are synthesized as MAC for the removal of formaldehyde (FA) and toluene in air through a combination of reactive adsorption and catalytic oxidation (RACO) at room temperature (RT). The best-performing composite (MAC-20: 20 % of MnO2) exhibits a 10 % breakthrough volume (BTV10%) of FA and toluene at 41.2 and 377 L g−1, respectively while realizing complete oxidation of FA and toluene into carbon dioxide (CO2) at 100 °C and 275 °C, respectively. The reaction kinetic rates (r) for 10 % removal efficiency of FA and toluene (XFA or T) at RT are estimated as 9.82E-02 and 3.20E-02 mmol g−1 h−1, respectively. The high performance of MAC-20 can be attributed to its enriched adsorption capacity of oxygen vacancy (OV) and the presence of adsorbed oxygen (OA), as shown by an Mn3+/Mn4+ ratio of 0.729 and an OA/lattice‑oxygen (OL) ratio of 1.50. The results of this study highlight the interactive roles of oxygen abundance and temperature in the generation of distinctive oxidation patterns for FA in reference to toluene. This study is expected to offer practical guidance for the implementation of RACO against diverse VOCs for efficient management of air quality.

Single Mn atom modulated molecular oxygen activation over TiO2 for photocatalytic formaldehyde oxidation

In single-atom catalysts, the atomically dispersed metal sites are pivotal for oxygen molecule activation. We hypothesize that dispersing single Mn atoms on TiO2 nanosheets may improve the photocatalytic oxidation of formaldehyde (HCHO) in the gas phase under ambient conditions. Density function theory (DFT) and experimental experiments were carried out to single Mn atoms not only improved the transfer of localized electrons and photogenerated electrons but also enhanced the activation/dissociation of O2 to generate monoatomic oxygen ions (O-) as the final reactive oxygen species (ROS). In photocatalytic experiments, Mn/TiO2 photocatalyst removed 100 % of HCHO at a low concentration of 7.6 ppm, and reaching excellent mineralization efficiency of over 99.6 %. According to the proposed reaction mechanism, O2 spontaneously adsorbs onto the Mn/TiO2 surface, forming two adsorbed O- after electron donation into the π2p* antibonding orbitals of O2. The adsorbed O- then reacts with gaseous HCHO to produce the key intermediate dioxymethylene (DOM), finally fulfilling a more favorable oxidation process on the Mn/TiO2 surface. This research illustrates the key role of O- in HCHO oxidation and paves the way for practical HCHO removal using TiO2-based photocatalysts.

Preparation of MnO2@MPIA catalysts with a controlled oxygen vacancy for the efficient catalytic oxidation of formaldehyde at room temperature

Preparation of MnO2@MPIA catalysts with a controlled oxygen vacancy for the efficient catalytic oxidation of formaldehyde at room temperature

Catalytic oxidation of formaldehyde by MnOx-decorated anatase TiO2{001}: Investigation of the effect of calcination temperature on catalytic activity and reaction mechanism

The removal of indoor formaldehyde (HCHO) is crucial for human health. The design of highly catalytically active nonprecious metal catalysts has major challenges, and the use of transition metal element modification to improve the catalytic performance is an effective strategy. In this study, the active component Mn was loaded on highly active crystalline anatase TiO2{001}, and the effect of the calcination temperature on the catalytic activity was investigated. The important influence of temperature on the catalyst valence distribution, surface active oxygen species, and content was thoroughly determined by characterization techniques, such as XPS, H2-TPR, and O2-TPD. The catalytic reaction process was further analyzed by in situ infrared technology to determine the reaction intermediates and to clarify the catalyst reaction poisoning mechanism; additionally, a reasonable HCHO catalytic reaction pathway was proposed with the combination of density function theory calculations. In addition, oxygen defects on the catalyst surface were determined by EPR, and based on theoretical calculations, the oxygen defects could further reduce the reaction energy barrier through the Langmuir-Hinshelwood mechanism. By exposing specific crystal surfaces and increasing the number of oxygen defects, the catalytic activity could be effectively improved; based on these results, our study provides a concept for the subsequent development of nonprecious metal catalysts.

Room temperature oxidation of gaseous formaldehyde over silver-doped manganese oxide catalyst

AbstractA wide amount of existing building materials and consumables contains formaldehyde (HCHO) that may be released as a gas even after installation. The produced gas may concentrate in housing and offices, leading to a long-term exposure of the occupants. Living in such an environment, even at low concentrations less than 0.5 ppm, may lead to carcinogenic effects and damages of the human central nervous system. As a consequence, the development of methods that oxidize and neutralize the formaldehyde at ambient temperature is welcome. The catalytic oxidation method at ambient temperature is preferred over other available techniques due to its ease of operation and high efficiency. In this work, different weight percentages, ranging from 1 up to 5%, of silver-doped manganese oxides (Ag/MnOx) were synthesized by a co-precipitation process followed by a calcination at 450 °C for 4 h. The XRD and BET analysis results show that the sample at 4% wt of Ag doped in the MnOx matrix exhibit highest crystallinity, surface area and highest dispersion values, very near to theoretical ones. The removal performance of HCHO was tested in a silicon wool bed continuous flow reactor characterized by an inner diameter of 4 mm and a length of 12.5 cm. At ambient temperature a removal efficiency and an amount of produced CO2 of 94% and 66%, respectively.

Choline degradation in Paracoccus denitrificans: identification of sources of formaldehyde.

Paracoccus denitrificans is a facultative methylotroph that can grow on methanol and methylamine as sole sources of carbon and energy. Both are oxidized to formaldehyde and then to formate, so growth on C1 substrates induces the expression of genes encoding enzymes required for the oxidation of formaldehyde and formate. This induction involves a histidine kinase response regulator pair (FlhSR) that is likely triggered by formaldehyde. Catabolism of some complex organic substrates (e.g., choline and L-proline betaine) also generates formaldehyde. Thus, flhS and flhR mutants that fail to induce expression of the formaldehyde catabolic enzymes cannot grow on methanol, methylamine, and choline. Choline is oxidized to glycine via glycine betaine, dimethylglycine, and sarcosine. By exploring flhSR growth phenotypes and the activities of a promoter and enzyme known to be upregulated by formaldehyde, we identify the oxidative demethylations of glycine betaine, dimethylglycine, and sarcosine as sources of formaldehyde. Growth on glycine betaine, dimethylglycine, and sarcosine is accompanied by the production of up to three, two, and one equivalents of formaldehyde, respectively. Genetic evidence implicates two orthologous monooxygenases in the oxidation of glycine betaine. Interestingly, one of these appears to be a bifunctional enzyme that also oxidizes L-proline betaine (stachydrine). We present preliminary evidence to suggest that growth on L-proline betaine induces expression of a formaldehyde dehydrogenase distinct from the enzyme induced during growth on other formaldehyde-generating substrates.IMPORTANCEThe bacterial degradation of one-carbon compounds (methanol and methylamine) and some complex multi-carbon compounds (e.g., choline) generates formaldehyde. Formaldehyde is toxic and must be removed, which can be done by oxidation to formate and then to carbon dioxide. These oxidations provide a source of energy; in some species, the CO2 thus generated can be assimilated into biomass. Using the Gram-negative bacterium Paracoccus denitrificans as the experimental model, we infer that oxidation of choline to glycine generates up to three equivalents of formaldehyde, and we identify the three steps in the catabolic pathway that are responsible. Our work sheds further light on metabolic pathways that are likely important in a variety of environmental contexts.

Effective formaldehyde elimination over pyrolusite-manganite hybrid catalysts promoted by Keggin acid decoration: Tungsten doping and chemically adsorbed active oxygen

A series of pyrolusite-manganite composites with five levels of phosphotungstic acid additions (HPWxMn, x indicating the added mass of phosphotungstic acid) were applied in the catalytic oxidation of 330–350 mg/m3 formaldehyde under ambient conditions. Different techniques were used to characterize the pristine composite and the best-performed HPW0.2Mn catalyst. Compared to the effects of hydrogen (replacing a small part of structural K+ ions) and phosphorus (not detected in the HPW0.2Mn catalyst) elements in phosphotungstic acid, the doping of tungsten would prefer to occur via forming W-O-Mn species, which significantly altered the crystallite growth and induced numerous defects. As to formaldehyde degradation, the best 91% conversion and 72% CO2 yield were achieved on HPW0.2Mn. The uniqueness of tungsten doping on boosting formaldehyde oxidation was expounded from the angles of intimate elemental interaction (XPS), redox behavior and molecular O2 activation (CO-TPR, UV-Vis DRS and O2-TPD). The incorporation of tungsten led to higher surface Mn3+ concentration, higher content of surface oxygen vacancies, better low-temperature reducibility and abounding chemically adsorbed oxygen species (They were proposed to be the dominant oxidants for formaldehyde oxidation in this study), which were well correlated with the sequence of catalytic activity. Finally, possible reaction pathways were examined by coupling the characterizations of used catalysts.

A new method for the preparation of MgAl layered double hydroxide-copper metal–organic frameworks structures: application to electrocatalytic oxidation of formaldehyde

In this research, we present a novel design protocol for the in-situ synthesis of MgAl layered double hydroxide-copper metal–organic frameworks (LDH-MOFs) nanocomposite based on the electrocoagulation process and chemical method. The overall goal in this project is the primary synthesis of para-phthalic acid (PTA) intercalated MgAl-LDH with Cu (II) ions to produce the paddle-wheel like Cu-(PTA) MOFs nanocrystals on/in the MgAl-LDH structure. The physicochemical properties of final product; Cu-(PTA) MOFs/MgAl-LDH, were characterized by the surface analysis and chemical identification methods (SEM, EDX, TEM, XRD, BET, FTIR, CHN, DLS, etc.). The Cu-(PTA) MOFs/MgAl-LDH nanocomposite was used to modification of the carbon paste electrode (CPE); Cu-(PTA) MOFs/MgAl-LDH/CPE. The electrochemical performance of Cu-(PTA) MOFs/MgAl-LDH/CPE was demonstrated through the utilization of electrochemical methods. The results show a stable redox behavior of the Cu (III)/Cu (II) at the surface of Cu-(PTA) MOFs/MgAl-LDH/CPE in alkaline medium (aqueous 0.1 M NaOH electrolyte). Then, the Cu-(PTA) MOFs/MgAl-LDH/CPE was used as a new electrocatalyst toward the oxidation of formaldehyde (FA). Electrochemical data show that the Cu-(PTA) MOFs/MgAl-LDH/CPE exhibits superior electrocatalytic performance on the oxidation of FA. Also the diffusion coefficient, exchange current density (J°) and mean value of catalytic rate constant (Kcat) were found to be 1.18 × 10–6 cm2 s−1, 23 mA cm-2 and 0.4537 × 104 cm3 mol−1 s−1, respectively. In general, it can be said the Cu-(PTA) MOFs/MgAl-LDHs is promising candidate for applications in direct formaldehyde fuel cells.

Cobalt enhanced (H/C-CdS)/CeO2 activity for visible light catalytic oxidation of formaldehyde at room temperature

The visible light catalytic oxidation of formaldehyde (HCHO) at room temperature is of great interest for improving the indoor air quality. Here, a cobalt (Co)-doped CdS-based catalyst ((H/C-CdS)/CeO2) with high visible light catalytic activity was successfully synthesized for HCHO removal at room temperature. Co addition enhanced the catalytic activity of (H/C-CdS)/CeO2, and the HCHO conversion rate reached 99.5 % for a 1 mg/L aqueous HCHO solution on the Co–(H/C-CdS)/CeO2 catalyst after 1 h at room temperature under visible light, which was greater than that of (H/C-CdS)/CeO2 (92.0 %). The (H/C-CdS)/CeO2 and Co–(H/C-CdS)/CeO2 catalysts were systemically characterized, and the results showed that the interfacial phase junction between the hexagonal (H) and cubic (C) phases of the CdS nanoparticles (NPs) and the synergistic effect of the type II heterojunction between the CdS NPs and CeO2 nanosheets (NSs) promoted the separation of e-/h+. Moreover, the addition of Co species strongly promoted the separation of photogenerated carriers. The excellent photocatalytic activity was attributed to the good dispersion of CdS NPs, which broadened the light absorption range, exposed more active sites, and provided close contact, decreasing the migration distance of photogenerated electron-hole pairs. After that, the visible light catalytic oxidation mechanism of HCHO on both (H/C-CdS)/CeO2 and Co–(H/C-CdS)/CeO2 followed the reaction pathway of HCHO to (CO2 + H2O).

Fabrication and Characterization of an Electrochemical Platform for Formaldehyde Oxidation, Based on Glassy Carbon Modified with Multi-Walled Carbon Nanotubes and Electrochemically Generated Palladium Nanoparticles.

This study outlines the fabrication process of an electrochemical platform utilizing glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNTs) and palladium nanoparticles (PdNPs). The MWCNTs were applied on the GCE surface using the drop-casting method and PdNPs were produced electrochemically by a potentiostatic method employing various programmed charges from an ammonium tetrachloropalladate(II) solution. The resulting GCEs modified with MWCNTs and PdNPs underwent comprehensive characterization for topographical and morphological attributes, utilizing atomic force microscopy and scanning electron microscopy along with energy-dispersive X-ray spectrometry. Electrochemical assessment of the GCE/MWCNTs/PdNPs involved cyclic voltammetry (CV) and electrochemical impedance spectroscopy conducted in perchloric acid solution. The findings revealed even dispersion of PdNPs, and depending on the electrodeposition parameters, PdNPs were produced within four size ranges, i.e., 10-30 nm, 20-40 nm, 50-60 nm, and 70-90 nm. Additionally, the electrocatalytic activity toward formaldehyde oxidation was assessed through CV. It was observed that an increase in the size of the PdNPs corresponded to enhanced catalytic activity in the formaldehyde oxidation reaction on the GCE/MWCNTs/PdNPs. Furthermore, satisfactory long-term stability over a period of 42 days was noticed for the GCE/MWCNTs/PDNPs(100) material which demonstrated the best electrocatalytic properties in the electrooxidation reaction of formaldehyde.

Multi‐Functional Formaldehyde‐Nitrate Batteries for Wastewater Refining, Electricity Generation, and Production of Ammonia and Formate

AbstractAs bulky pollutants in industrial and agricultural wastewater, nitrate and formaldehyde pose serious threats to the human health and ecosystem. Current purification technologies including chemical and bio‐/photo‐/electro‐chemical methods, are generally high‐cost, time‐consuming, or energy‐intensive. Here, we report a novel formaldehyde‐nitrate battery by pairing anodic formaldehyde oxidation with cathodic nitrate reduction, which simultaneously enables wastewater purification, electricity generation, and the production of high‐value‐added ammonia and formate. As a result, the formaldehyde‐nitrate battery remarkably exhibits an open‐circuit voltage of 0.75 V, a peak power density of 3.38 mW cm−2 and the yield rates of 32.7 mg h−1 cm−2 for ammonia and 889.4 mg h−1 cm−2 for formate. In a large‐scale formaldehyde‐nitrate battery (25 cm2), 99.9 % of nitrate and 99.8 % of formaldehyde are removed from simulated industrial wastewater and the electricity of 2.03 W⋅h per day is generated. Moreover, the design of such a multi‐functional battery is universally applicable to the coupling of NO3− or NO2− reduction with various aldehyde oxidization, paving a new avenue for wastewater purification and chemical manufacturing.

Multi-Functional Formaldehyde-Nitrate Batteries for Wastewater Refining, Electricity Generation, and Production of Ammonia and Formate.

As bulky pollutants in industrial and agricultural wastewater, nitrate and formaldehyde pose serious threats to the human health and ecosystem. Current purification technologies including chemical and bio-/photo-/electro-chemical methods, are generally high-cost, time-consuming, or energy-intensive. Here, we report a novel formaldehyde-nitrate battery by pairing anodic formaldehyde oxidation with cathodic nitrate reduction, which simultaneously enables wastewater purification, electricity generation, and the production of high-value-added ammonia and formate. As a result, the formaldehyde-nitrate battery remarkably exhibits an open-circuit voltage of 0.75 V, a peak power density of 3.38 mW cm-2 and the yield rates of 32.7 mg h-1  cm-2 for ammonia and 889.4 mg h-1  cm-2 for formate. In a large-scale formaldehyde-nitrate battery (25 cm2 ), 99.9 % of nitrate and 99.8 % of formaldehyde are removed from simulated industrial wastewater and the electricity of 2.03 W⋅h per day is generated. Moreover, the design of such a multi-functional battery is universally applicable to the coupling of NO3 - or NO2 - reduction with various aldehyde oxidization, paving a new avenue for wastewater purification and chemical manufacturing.

Noble-Metal-Based Catalysts on a Scale from Nanoparticles to Subnanoclusters and Single Atoms for Formaldehyde Oxidation at Room Temperature: A Review

Noble-Metal-Based Catalysts on a Scale from Nanoparticles to Subnanoclusters and Single Atoms for Formaldehyde Oxidation at Room Temperature: A Review

Surficial engineering of active hydroxyls for ambient formaldehyde oxidation via enhanced Lewis acidity over Zr-doped cryptomelane materials

Lewis acids of solid catalysts have been featured for a pivotal role in promoting various reactions. Regarding the oxidation protocol to remove formaldehyde, the inherent drawback of the best-studied MnO2 materials in acidic sites has eventually caused deficiency of active hydroxyls to sustain low-temperature activity. Herein, the cryptomelane-type MnO2 was targeted and it was tuned via incorporation of Zr metal, exhibiting great advances in not only the complete HCHO-to-CO2 degradation but also cycling performance. Zr species were existent in doping state in the MnO2 lattice, rendering lower crystallinity and breaking the regular growth of MnO2 crystallites, which thereby tripled surface area and created larger volume of smaller mesopores. Meantime, the local electronic properties of Mn atoms were also changed by Zr doping, i.e., more low-valence Mn species were formed due to the electron transfer from Zr to Mn. The results of infrared studies demonstrate the higher possession of Lewis acid sites on ZrMn, and this high degree of electrophilic agents favored the production of hydroxyl species. Furthermore, the reactivity of surface hydroxyls, as investigated by CO temperature programmed reduction and temperature programmed desorption of adsorbed O2, was obviously improved as well after Zr modification. It is speculated jointly with the characterizations of the post-reaction catalysts that the accelerated production of active hydroxyls helped rapidly convert formaldehyde into key intermediate—formate, which was then degraded into CO2, avoiding the side reaction path with undesired intermediate—hydrocarbonate—over the pristine MnO2, where active sites were blocked and formaldehyde oxidation was inhibited. Additionally, Zr decoration could stabilize Lewis acidity to be more resistant to heat degeneration, and this merit brought about advantageous thermal recyclability for cycled application.