Catalytic Reduction Research Articles

Recent Advances in NO Reduction with NH3 and CO Over Cu-Ce Bimetallic and Derived Catalysts

Sintering flue gas contains significant amounts of harmful gases, such as carbon monoxide and nitrogen oxides (NOx), which pose severe threats to the ecological environment and human health. Selective catalytic reduction (SCR) technology is widely employed for the removal of nitrogen oxides, with copper-cerium-based bimetallic catalysts and their derivatives demonstrating excellent catalytic efficiency in SCR reactions, primarily due to the significant synergistic effect between copper and cerium. This paper summarizes the main factors affecting the catalytic performance of Cu-Ce-based bimetallic catalysts and their derivatives in the selective catalytic reduction of ammonia and carbon monoxide. Key considerations include various preparation methods, doping of active components, and the effects of loading catalysts on different supports. This paper also analyzes the influence of surface oxygen vacancies, redox capacity, acidity, and specific surface area on catalytic performance. Additionally, the anti-poisoning performance and reaction mechanisms of the catalysts are discussed. Finally, the paper proposes strategies for designing high-activity and high-stability catalysts, considering the development prospects and challenges of Cu-Ce-based bimetallic catalysts and their derivatives, with the aim of providing theoretical guidance for optimizing Cu-Ce-based catalysts and promoting their industrial applications.

Light‐Responsive Aldehyde‐Reduction Catalysis Through Catalyst Encapsulation

We report a light‐responsive tetrahedral metal–organic capsule that binds a perrhenate catalyst, which is released selectively upon irradiation with 350 nm light, turning on the catalytic reduction of organic carbonyls by hydrosilanes. The catalytic activity can be switched off by heating at 75 °C for 2.5 h, which stimulates capsule reformation and catalyst re‐encapsulation. Multiple on‐off cycles were shown, with a clear relationship between product yield and light irradiation time. Encapsulation thus enables the coupling of light‐responsiveness to catalysis in a manner that might be generalized to other catalysts and capsules.

Homobimetallic Ruthenium(II) Complexes Catalysed Selective Transfer Hydrogenation of Aldehydes in Water

Herein we report chemoselective transfer hydrogenation (TH) of aldehydes in aqueous medium using a series of homobimetallic Ru(II) catalysts. Two homobimetallic complexes (Ru1 and Ru3) and one monometallic complex (Ru2) have been employed in the catalytic reduction of aldehydes. Bimetallic complex [(p‐cymene)2(RuCl)2L3] (Ru3) is obtained from the reaction of Schiff base ligand 2,2'‐((1E,1'E)‐((3,3',5,5'‐tetraisopropyl‐[1,1'‐biphenyl]‐4,4'diyl)bis(azaneylylidene))bis(methaneylylidene))bis(4‐bromophenol) (H2L3) and characterized by various spectroscopic and analytical techniques. The use of formic acid/formate buffer as the hydride source and a catalyst loading of 0.01 mol% of Ru1 or Ru3 resulted in the conversion of various aldehydes to the corresponding alcohols in good to excellent yield. This method is very efficient for selective reduction of aldehydes in the presence of other reducible functional groups. A loading of 0.0001 mol% of Ru1 catalyst is sufficient to achieve a turnover frequency (TOF) of 5.5× 105 h‐1. Furthermore, the catalyst can been recycled and reused for six consecutives cycles without sacrificing the efficiency. A comparison of results obtained between bimetallic and monometallic complexes offers valuable insights into the distinct reactivity patterns of the bimetallic complexes, presumably originating from a cooperative effect. We have explored the mechanistic pathway using DFT methods.

Light‐Responsive Aldehyde‐Reduction Catalysis Through Catalyst Encapsulation

We report a light‐responsive tetrahedral metal–organic capsule that binds a perrhenate catalyst, which is released selectively upon irradiation with 350 nm light, turning on the catalytic reduction of organic carbonyls by hydrosilanes. The catalytic activity can be switched off by heating at 75 °C for 2.5 h, which stimulates capsule reformation and catalyst re‐encapsulation. Multiple on‐off cycles were shown, with a clear relationship between product yield and light irradiation time. Encapsulation thus enables the coupling of light‐responsiveness to catalysis in a manner that might be generalized to other catalysts and capsules.

Chiral SPINOL‐Derived Borophosphate‐Catalyzed Asymmetric 1,4‐Reduction of Exocyclic α,β‐Unsaturated Ketones

AbstractAn asymmetric 1,4‐reduction of exocyclic α,β‐unsaturated ketones, yielding diverse optically active α‐substituted tetralones, has been achieved using a chiral SPINOL‐derived borophosphate catalyst. The enantioselectivity‐determining step of the reaction involves the protonation of a highly active boron enolates intermediate. This catalytic reduction system, comprising chiral SPINOL‐derived borophosphate and pinacolborane, has potential for broader application in other asymmetric reduction reactions.

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

Revolutionary ZVI-Entrapped Sol–Gel Silica Matrices: Efficient Catalytic Reduction of High-Concentration Halo-Organic Compounds—Addressing Bromoacetic Acid Contamination in Industrial Wastewaters

The de-halogenation of highly concentrated halo-organic compounds using Zero Valent Iron entrapped in silica matrices as a catalyst was investigated. This study aimed to evaluate the effectiveness of the Zero Valent Iron-entrapped organically modified silica matrices in transforming highly concentrated hazardous halogenated compounds into environmentally benign materials in the presence of BH4−. The Zero Valent Iron-entrapped silica gel matrices were synthesized using the sol–gel method. The de-halogenation products were analyzed using high-performance liquid chromatography. The results suggest that the Zero Valent Iron-entrapped silica matrices are effective catalysts in the de-halogenation reaction of halo-organics by BH4− with 100% efficiency. The current work also highlights the complete de-bromination of harmful wastewater generated by the bromoacetic acid manufacturing industry using Zero Valent Iron-entrapped silica matrices. Therefore, Zero Valent Iron-entrapped silica matrices can be considered potential candidates for the catalytic removal of highly concentrated halo-organic compounds from contaminated water. This technology can play a crucial role in reducing the environmental impact of hazardous substances.

Enabling Unfavorable Hydroamination Reactions Using a Chemoselective N-O Bond Reduction.

Despite major advances, intramolecular alkene hydroamination reactions often face limitations. Herein, a redox-enabled process featuring oxidation of an amine to a hydroxylamine, a concerted hydroamination step, followed by catalytic reduction of N-oxide is shown to be broadly applicable. Catalyst screening and optimization showed that a K2OsO2(OH)4-pinacol complex rapidly and chemoselectively reduces the N-oxide cycloadduct in the presence of hydroxylamine and dimethyl sulfoxide. This selectivity was exploited to drive the equilibria toward complex products.

Research Progress in the Composition and Performance of Mn-Based Low-Temperature Selective Catalytic Reduction Catalysts

NH3 selective catalytic reduction (NH3-SCR) is the most prevalent and effective method for removing nitrogen oxides. Over the past few decades, manganese (Mn)-based catalysts have demonstrated strong catalytic activity and have been extensively studied for low-temperature NH3-SCR reactions. This paper provides an in-depth introduction to four forms of Mn-based catalysts: single manganese oxide-based catalysts, binary Mn-based metal oxide catalysts, ternary and multivariate Mn-based metal oxide catalysts, and nano-Mn-based catalysts. Advances have been made in enhancing Mn-based catalysts’ redox performance and acidity, increasing the active component’s dispersion, lowering binding energy, enlarging specific surface area, raising the Mn4+/Mn3+ ratio, and enriching surface adsorbed oxygen by optimizing preparation methods, altering the oxidation state of active components, modifying crystal phases, and adjusting morphology and dispersion, along with various metal modifications. The mechanism of low-temperature NH3-SCR reactions has been elucidated using various characterization techniques. Finally, the research directions and future prospects of Mn-based catalysts for low-temperature NH3-SCR reactions are discussed, aiming to accelerate the commercial application of new Mn-based catalysts.

The next challenge in emissions control for heavy-duty diesel vehicles: From NOx to N2O

Vehicle emissions are a major source of greenhouse gases globally. Dual selective catalytic reduction (SCR), an advanced version of single SCR, is crucial under stricter nitrogen oxide (NOx) emission standards for heavy-duty diesel vehicles (HDDVs). However, the emission characteristics of nitrous oxide (N2O), a byproduct of SCR and a potent greenhouse gas, remain unclear. This study investigates the N2O emissions from HDDVs equipped with single or dual SCR systems using heavy-duty chassis dynamometers under various ambient temperatures, altitudes, and loading masses. The results showed that the brake-specific emissions (EFb) of N2O from HDDVs with single and dual SCRs were 76.28–269.65 mg/kWh and 147.50–170.22 mg/kWh, respectively. Notably, the dual SCR-equipped HDDV emitted 6–22 times more N2O than NOx under all tested conditions. As ambient temperature increased from −10 °C to 25 °C and from 25 °C to 40 °C, the average distance-based emission factors (EFd) of N2O for the single SCR-equipped HDDV increased by 87.73% and 48.26%, respectively. However, the variation was not significant for the dual SCR-equipped HDDV. Under half- and full-load conditions, the average EFd of N2O for the single SCR-equipped HDDV increased by 47.57% and 110.92%, respectively, compared to those without loading. Similarly, N2O emissions for dual SCR-equipped HDDV increased by 41.40% and 65.37% under the same loading variations. As altitude increased from 0 m to 3000 m, the average EFd of N2O for the single SCR-equipped HDDV decreased by 64.31%. Additionally, N2O emissions were significantly affected by SCR temperature, engine power, and nitric oxide (NO)/nitrogen dioxide (NO2) ratio. These findings are crucial for setting future greenhouse gas limits of HDDVs and informing carbon reduction strategies.

DFT-guided synthesis of N, B dual-doped porous carbon from saccharina japonica for enhanced oxygen reduction catalysis

IntroductionThe oxygen reduction reaction (ORR) is a crucial determinant of the energy transformation capacity of fuel cells. This study investigates the performance of N and B dual-doped carbon in ORR.MethodsSix models using density functional theory (DFT) are developed to compare the performance of different doping strategies. A highly efficient dual-doped carbon ORR catalyst (S-850-1) is synthesized from Saccharina japonica, containing 4.54 at% N and 1.05 at% B atom.ResultsElectrochemical analysis reveals that S-850-1 significantly outperforms the nitrogen mono-doped carbon S-850, exhibiting a higher half-wave potential of 0.861 V and a greater limited current density of −5.60 mA cm⁻2, compared to S-850’s 0.838 V and −5.24 mA cm⁻2. Furthermore, S-850-1 surpasses the performance of 20% Pt/C, demonstrating enhanced durability and exceptional resistance to CO and methanol. The 1.40 V open circuit voltage produced by S-850-1 when integrated into a Zn-air battery can power an LED light.DiscussionBoth theoretical and practical evaluations validate the excellent ORR performance of nitrogen and boron dual-doped carbon, as evidenced by the agreement between the electrochemical results and DFT calculations. This work not only extends the range of ORR catalysts derived from biomass but also provides guidance on creating and producing affordable, effective catalysts that utilize natural resources.

A solving new method for the urea-selective catalytic reduction (SCR) system in a diesel engine using coupled hyperbolic-parabolic partial differential equations (PDEs)

To control the diesel engine urea SCR system with high accuracy, firstly, the partial differential equations of the SCR system are simplified through variable substitution and the method of characteristic lines to eliminate the partial derivative terms of the hyperbolic partial differential equations in the flow direction. The backward difference method is used to solve the problem, and the adaptive time step is adjusted to improve computational efficiency. Secondly, the Levenberg-Marquardt algorithm is applied to identify the model parameters per second based on the 1800-s test bench data. By combining the experimental data with the parameter identification results, this paper calculated the downstream NOx concentration with 99.5 % accuracy. Finally, the 1800s transient test data was applied to a commonly used single-state SCR control model, and cell numbers 1–4 of the cases were numerically simulated. It was found that the reduced-order model had a computation time of 1 s but was less accurate. When the test data was applied to the model presented in this study, the calculation time was 27s, and the model's calculation results show that the average error of the downstream NOx concentration is 16.95 ppm, which is 14.3 ppm lower than that of the two-cell one-state model.

Catalytic reduction of p-nitrophenol and Eosin Yellow by lemongrass tea-stabilized copper nanoparticles

ABSTRACT Green synthesis of nanoparticles for catalytic applications remains of continued interest, especially for reactions that would occur on an industrial scale or that may be of environmental significance. Here, ultrasmall 2.1-nm copper nanoparticles were synthesized under ambient conditions using a copper sulfate pentahydrate precursor and lemongrass extract as a reducing and capping agent. Their potential to act as catalysts was tested using model reactions: the sodium borohydride reduction reactions of p-nitrophenol and Eosin Yellow. Kinetics measurements were obtained with visible time-course spectroscopy and showed that copper nanoparticles effectively catalyzed both reactions. Temperature dependence followed Arrhenius behavior, indicating the catalyst surface was accessible to reactants. Activation energies of 59.2 and 38.5 kJ/mol were obtained for the reduction reactions of p-nitrophenol and Eosin Yellow, respectively. Large frequency factors for both reactions were found, implying large numbers of catalytic sites and/or facilitation of reaction by capping agents. This copper nanoparticle catalyst prepared via green synthesis demonstrates reproducible reduction behavior for two model reactions and observed rate constants that compare favorably with other copper nanoparticle catalysts, particularly in terms of rate constants normalized for available surface area and including catalysts produced via traditional synthetic methods.

An Ambient Measurement Technique for Vehicle Emission Quantification and Concentration Source Apportionment.

We develop a new technique called plume regression where fast response instruments located at the roadside are used to measure exhaust plumes of passing vehicles. The approach is used to generate highly disaggregated vehicle emissions information by vehicle type, which compares well with traditional vehicle emission remote sensing. Additionally, the technique provides valuable new information on ambient concentration source apportionment by vehicle type. The technique is flexible enough to consider a wide range of air pollutants and be deployed at roadside ambient monitoring locations. The new approach is used to quantify emissions and concentration source apportionment for ammonia (NH3) and nitrogen oxides (NOx). We find that emissions of NH3 are generally very well controlled from diesel vehicles including those with selective catalytic reduction systems that use NH3 to reduce emissions of NOx. By contrast, gasoline passenger cars are shown to be the dominant contributor to NH3 emissions, which increase with vehicle mileage. Average fuel-specific NH3 emission factors for gasoline vehicles range from 0.3 to 1.2 g kg-1, while diesel vehicle emission factors remain below 0.06 g kg-1, with the exception of Euro VI buses with the latest regulatory provisions (0.5 g kg-1).

Optimizing catalytic performance: Reduction of organic dyes using synthesized Fe3O4@AC magnetic nano-catalyst

This article presents a sustainable method for the catalytic reduction of both simple and binary dye systems using magnetic activated carbon (Fe3O4@AC) synthesized from almond shells, an agricultural waste biomass. The reduction of methylene blue (MB) and Congo red (CR) was investigated in the presence of NaBH4, and a series of physical-chemical experiments were conducted to elucidate the mechanism of dye conversion and its performance. The results confirmed the successful synthesis of Fe3O4 nanoparticles on the activated carbon surface. The calculated rate constants in a simple system were 0.34 min⁻1 for MB and 0.25 min⁻1 for CR, in the binary system, the Fe3O4@AC catalyst demonstrated enhanced selectivity for the cationic MB dye, attributable to the robust, attractive surface charge. The study aimed to enhance catalytic performance by employing optimization curves generated from a three-level Box-Behnken Design (BBD) simulation. Experimental results indicated that the optimal catalyst dose, dye concentration, and reaction duration were 4–7 mg, 80–120 mg/L, and 5–20 min, respectively. Response surface methodology (RSM) was developed by processing the findings from 17 replicated experiments using a two-quadratic polynomial model, establishing a functional link between the experimental parameters and MB conversion. Optimal conditions for MB conversion were determined to be 7 mg of catalyst, 80 mg/L of MB concentration, and a reaction time of 12.5 minutes, resulting in an estimated conversion rate of 99.99 %. This prediction was validated by experimental findings, with regression analysis confirming a high correlation (R2 > 0.99) between the predicted and observed values. Additionally, the Fe3O4@AC catalyst demonstrated good recyclability and stable performance over three consecutive cycles, maintaining high conversion efficiency without loss of performance. These findings demonstrate that Fe3O4@AC is a viable approach for the rapid and efficient remediation of dyes in water.

Harnessing Electrolyte Chemistry to Advance Oxygen Reduction Catalysis for Fuel Cells and Electrosynthesis

Harnessing Electrolyte Chemistry to Advance Oxygen Reduction Catalysis for Fuel Cells and Electrosynthesis

A robust floating oxygen-doped graphitic carbon nitride sheet for efficient photocatalytic CO2 conversion

Photocatalytic CO2 reduction offers a promising approach for converting CO2 into valuable chemicals. However, typical conversion systems suffer from inefficient CO2 mass transfer and complex recycling processes. In this study, we developed a floating sheet as a robust photocatalytic CO2 conversion system by integrating graphitic carbon nitride (CN) nanosheets onto polytetrafluoroethylene (PTFE) fiber membrane, followed by oxygen (O) doping into the CN (CN-O) via oxygen-plasma treatment. The floatable CN-O/PTFE sheet exhibits slight wettability in water under 0.25 MPa of CO2 pressure in our reactor system, facilitating the delivery of dissolved CO2 to the CN-O photocatalyst surface. O-doping enhances the visible light absorption and improves the separation and transport efficiency of photogenerated electrons and holes due to O-doping-induced states in CN. Consequently, the floating CN-O/PTFE system achieves an exceptional photocatalytic CO2 conversion rate of 102.3 μmol g-1h−1, approximately 4.8 times higher than a conventional CN-powder dispersion system in water. Moreover, the sheet demonstrates excellent cycling durability, with no significant exfoliation of the catalytic layer or reduction in CO2 photoreduction activity after 20 consecutive cycles. This study presents a novel approach to designing photocatalytic systems for efficient CO2 conversion.

TM@MoSSe (TM = Ni, Fe) as novel electrocatalysts for reduction of CO2 to CO: A DFT study

It is crucial to develop highly efficient, selective and low-overpotential electrocatalysts for CO2 reduction. This paper proposes an efficient iron and nickel single-atom catalyst using Janus MoSSe as the substrate to reduce CO2 to CO by using DFT calculations. The adsorption of a single TM atom like Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt on Janus MoSSe monolayer results in a decrease in band gap, which may accelerate the catalytic CO2 reduction. The excellent catalytic activity of Fe@MoSSe and Ni@MoSSe is owing to the high d-band center and hence the strong TM-CO2 bonding. The asymmetric structure of Janus MoSSe creates the local built-in electric field, which further increases by about 8% or 0.8% after the adsorption of single Ni or Fe atom so as to afford the better electrocatalytic performances for reduction of CO2 to CO in both TM modified systems. So, this work proposes the catalysts Fe@MoSSe and Ni@MoSSe with good selectivity and activity for CO2 reduction by revealing their underlying mechanisms, and Janus MoSSe may be used as a potential substrate material for CO2 reduction catalysts.

Methanol-assisted NO oxidation under an oxygen atmosphere for efficient denitration: Experiments and ReaxFF-MD simulations

The development of selective catalytic reduction technologies for controlling nitrogen oxide (NOx) emissions in flue gas is hampered by high equipment and catalyst costs. In this study, a catalyst-free and efficient denitration process using methanol and oxygen as reactants was developed. Various gas atmospheres with differing concentrations were investigated to remove NO without catalysts. The addition of methanol significantly enhanced NO removal efficiency, reaching 94.6 % at 550 °C, with 55.1 % of NO converted to NO2, which can be absorbed by downstream alkali solutions. Reactive force field molecular dynamics (ReaxFF-MD) simulations were employed to analyze the atomic level NO oxidation mechanism in the CH3OH/NO/O2/H2O homogeneous reaction system. The simulation revealed the generation pathway of three key oxidizing intermediates (OH, HO2, and H2O2) and their roles in NO oxidation. This study offers critical insights into developing a cost-effective denitration process, highlighting the potential for improved NOx emission control.

A systematic study on Au-PDA@Fe3O4 core-shell catalysts for enhanced catalytic reduction of 4-nitrophenol

The development of nanogold catalysts with high activity and high stability is of great significance for their industrial applications. In this paper, Au-PDA@Fe3O4 catalysts were prepared through the gold sol adsorption method. First, micron-sized magnetic Fe3O4 spheres were synthesized via a solvothermal method, serving as the core to endow the catalyst with excellent recyclability. Subsequently, a layer of polydopamine (PDA) shell was polymerized on the magnetic core surface. By controlling the timing of introducing the gold sol containing Au nanoparticles (NPs), the spatial position of Au NPs within the PDA layer was regulated, leading to a series of magnetic core-shell nano gold catalysts with varying spatial positions of Au. Using the 4-nitrophenol (4-NP) hydrogenation as the probe, the influence of Au spatial position, Au size, and other conditions on the catalytic performance was investigated. Results showed that, in the prepared Au-PDA@Fe3O4-16 catalyst, the Au NPs are encapsulated within the PDA shell and positioned close to the outer layer. This not only provides remarkable stability to the Au NPs but also maintains their proximity to the surface of the PDA shell, allowing easier access of the substrate 4-NP to the Au NPs and conferring good reactivity upon the catalyst. The strong electron metal-support interaction between PDA and Au enables PDA to effectively stabilize Au NPs. The prepared Au-PDA@Fe3O4-16 catalyst exhibits excellent stability, maintaining a high conversion rate of 91% even after 14 cycles of use. Our findings not only deepen the understanding of the catalytic mechanisms involved but also pave the path towards the creation of highly efficient and robust gold-based catalysts, facilitating their widespread utilization in industrial applications.