Inhibiting the Formation of Toxic HCN Induced by C3H6 Coexistence and Enhancing C3H6 Resistance of Cu-Zeolite in the NH3-SCR Reaction.

The presence of light hydrocarbons (HCs) in diesel exhaust, specifically C3H6, significantly affects the performance of the state-of-the-art Cu-SSZ-13 zeolite NH3-SCR catalysts. It also leads to the formation of highly toxic HCN, posing risks to the environment and human health. In this work, the highly toxic HCN formation is inhibited, and the C3H6 resistance of Cu-SSZ-13 is improved by secondary metal modification via doping with rare earth/transition metal elements. Upon introduction of C3H6, the activity of Cu-SSZ-13 significantly decreases at medium-high temperatures. This is primarily due to the competitive reaction between C3H6 and NH3, which compete for the NH3 reductant required in the NH3-SCR reaction, resulting in the production of HCN. The unfavorable effect is alleviated on the modified catalysts due to their enhanced oxidation capabilities toward C3H6 and the HCHO intermediate, facilitating the complete oxidation of C3H6 to COx. This inhibits the undesirable partial oxidation reaction between C3H6 and NH3, thereby improving the activity of Cu-SSZ-13 at medium to high temperatures and significantly reducing the formation of highly toxic HCN.

Facilely Fabricated Single-Site Ptδ+-O(OH)x- Species Associated with Alkali on Zirconia Exhibiting Superior Catalytic Oxidation Reactivity.

Fabrication of robust isolated atom catalysts has been a research hotspot in the environment catalysis field for the removal of various contaminants, but there are still challenges in improving the reactivity and stability. Herein, through facile doping alkali metals in Pt catalyst on zirconia (Pt-Na/ZrO2), the atomically dispersed Ptδ+-O(OH)x- associated with alkali metal via oxygen bridge was successfully fabricated. This novel catalyst presented remarkably higher CO and hydrocarbon (HCs: C3H8, C7H8, C3H6, and CH4) oxidation activity than its counterpart (Pt/ZrO2). Systematically direct and solid evidence from experiments and density functional theory calculations demonstrated that the fabricated electron-rich Ptδ+-O(OH)x- related to Na species rather than the original Ptδ+-O(OH)x-, serving as the catalytically active species, can readily react with CO adsorbed on Ptδ+ to produce CO2 with significantly decreasing energy barrier in the rate-determining step from 1.97 to 0.93 eV. Additionally, owing to the strongly adsorbed and activated water by Na species, those fabricated single-site Ptδ+-O(OH)x- linked by Na species could be easily regenerated during the oxidation reaction, thus considerably boosting its oxidation reactivity and durability. Such facile construction of the alkali ion-linked active hydroxyl group was also realized by Li and K modification which could guide to the design of efficient catalysts for the removal of CO and HCs from industrial exhaust.

Tailoring the Electronic Metal-Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation.

Metal-modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO2 support through strong electronic metal-support interactions (EMSIs), overcoming the activity-selectivity trade-off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C2H4) and oxygen (O2) and facilitating EO desorption, resulting in high C2H4 conversion. Meanwhile, the increased number of positively charge Ag+ lowers the energy barrier for C2H4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.

Tandem pyrolysis-catalytic upgrading of plastic waste towards kerosene-range products using Si-pillared vermiculite with transition metal modification.

The transformation of waste plastics to fuel products is an appealing strategy to address plastic-associated environmental and energy issues. In this study, a tandem pyrolysis-catalytic upgrading approach, using a series of mono-/bitransition-metal-modified Si-pillared vermiculite catalysts, was adopted to transform disposable grocery bags (i.e., a polyethylene-based material) to kerosene-range fuels. The results revealed that the silicon pillars contributed to the catalyst's excellent thermal stability to withstand temperatures of up to 1000 °C, while the transition-metallic species (e.g., Co/Ni/Fe) contributed to the fine-tuning of the catalyst's acidity and porosity. Specifically, Co-Fe/Si-pillared vermiculite (SPV) (5:5) produced the highest yield of oil products (75.7 wt%), with alkane and aromatic selectivities of 57.5% and 27.8%, respectively, resembling the composition of kerosene. The catalyst's high selectivities for the targeted products were attributed to the controllable acidity and porosity, enabling a balance to be achieved between these two properties. Pathways were proposed for the tandem pyrolysis in the presence of Co-Fe/SPV. The vermiculite-based catalysts showed satisfactory reusability following regeneration. Beyond polyethylene-based plastics, these catalysts are also applicable to the pyrolysis of other plastic feedstocks. Because vermiculite is a low-cost material, the developed catalyst has good commercialization potential for a wide spectrum of waste-to-energy conversions.

Enhanced phosphate adsorption studies on several metal-modified aluminum sludge: preparation optimization, adsorption behavior, and mechanistic insight.

To solve the problems such as water eutrophication caused by excess phosphorus, the potential residual value of aluminum sludge was fully exploited and its phosphate adsorption capacity was further improved. In this study, twelve metal-modified aluminum sludge materials were prepared by co-precipitation method. Among them, Ce-WTR, La-WTR, Y-WTR, Zr-WTR, and Zn-WTR showed excellent adsorption capacity for phosphate. The adsorption performance of Ce-WTR on phosphate was twice that of the native sludge. The enhanced adsorption mechanism of metal modification on phosphate was investigated. The characterization results showed that the increase in specific surface area after metal modification was 9.64, 7.5, 7.29, 3, and 1.5 times, respectively. The adsorption of phosphate by WTR and Zn-WTR was in the accordance with Langmuir model, while the others were more following the Freundlich model (R2 > 0.991). The effects of dosage, pH, and anion on phosphate adsorption were investigated. The surface hydroxyl groups and metal (hydrogen) oxides played an important role in the adsorption process. The adsorption mechanism involves physical adsorption, electrostatic attraction, ligand exchange, and hydrogen bonding. This study provides new ideas for the resource utilization of aluminum sludge and theoretical support for preparing novel adsorbents for efficient phosphate removal.

Niobium- and cobalt-modified dual-source-derived porous carbon with a honeycomb-like stable structure for supercapacitor and hydrogen evolution reaction.

Designing porous carbon materials with tailored architecture and appropriate compositions is essential for supercapacitor (SC) and hydrogen evolution reaction (HER). Herein, Nb/Co-modified dual-source porous carbon (Nb/Co-DSPC) with a honeycomb structure was obtained by introducing a secondary carbon source (Co/Zn-ZIF) and transition metal Nb into activated Typha carbon (ATC). The addition of a secondary carbon source and Nb resulted in superior specific surface area (1272.38 m2/g), excellent hydrophilicity (34.73°) and abundant bimetallic active sites (Nb/Co-Nx) in Nb/Co-DSPC, providing excellent charge storage capacity and electrocatalytic activity. The Nb/Co-DSPC electrode displayed an outstanding capacitance of 337 F/g at 0.5 A/g and showed excellent stability after 15,000 charge-discharge cycles. In addition, Nb/Co-DSPC shows an overpotential of 114 mV at 10 mA cm-2, better than those of Co-DSPC (139 mV) and ATC (162 mV) alone. This study offers a reliable strategy for advanced multifunctional porous carbon electrode materials preparations.

Ecotoxicological characterization of engineered biochars produced from different feedstock and temperatures.

Biochar (BC) engineering, which has recently gained a lot of interest, allows designing the functional materials. BC modification improves the properties of pristine biochar, especially in terms of adsorption parameters. An interesting type of modification is the introduction of metals into the BC's structure. There is a knowledge gap regarding the effects of modified BC (e.g., BC-Mg, BC-Zn) on organisms. The aim of this study was the ecotoxicological evaluation of BC-Mg and BC-Zn composites, received under diverse conditions from willow or sewage sludge at 500 or 700 °C. The ecotoxicological tests with bacteria Vibrio fischeri (V. fischeri) and invertebrates Folsomia candida (F. candida) were applied to determine the toxicity of BC. The content of toxic substances (e.g., polycyclic aromatic hydrocarbons (PAHs), heavy metals (HMs), environmentally persistent free radicals (EPFRs)) in BC were also determined and compared with ecotoxicological parameters. The ecotoxicity of studied BCs depends on many variables: feedstock type, pyrolysis temperature and the modification type. The Zn and Mg modification reduced (from 28 to 63 %) the total Æ©16 PAHs content in willow-derived BCs while in SL-derived BCs the total Æ©16 PAHs content was even 1.5-3 times higher compared to pristine BCs. The Zn modified willow-derived BCs affected positively on F. candida reproduction but showed inhibition of luminescence V. fischeri. BC-Mg exhibited harmful effect to F. candida. The ecotoxicological assessment carried out sheds light on the potential toxicity of BC-Zn and BC-Mg composites, which are widely used in the removal of heavy metals, pharmaceuticals, dyes from waters and soils.

Research on alkali metal-modified Pd catalyst for oxygen removal from propylene.

A series of alkali metal (Li, Na, and K)-modified Pd catalysts and Pd/Al2O3 were prepared and used to remove oxygen in a propylene flow with hydrogen's existence. The results showed that the alkali metals could enhance the performance of the Pd catalysts and the effect followed the order of K > Na > Li. X-Ray diffraction (XRD), N2-physisorption, transmission electron microscopy (TEM), hydrogen temperature programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were carried out to investigate the alkali metal-modified Pd catalysts and the promotional effect mechanism was explained. The results showed that alkali metal modification increased the electron density of Pd atoms to induce the negatively charged Pd species, which could enhance the adsorption of oxygen while weakening the adsorption of propylene, and then enhance the performance of the modified catalysts for oxygen removal from unsaturated hydrocarbon. The Pd-K/A catalyst performed the best on both oxygen removal and propylene hydrogenation inhibition.

Effect of Bimetal Element Doping on the Low-Temperature Activity of Manganese-Based Catalysts for NH3-SCR.

A series of novel Mn6Zr1-xCox denitrification catalysts were prepared by the co-precipitation method. The effect of co-modification of MnOx catalyst by zirconium and cobalt on the performance of NH3-SCR was studied by doping transition metal cobalt into the Mn6Zr1 catalyst. The ternary oxide catalyst Mn6Zr0.3Co0.7 can reach about 90% of NOx conversion in a reaction temperature range of 100-275°C, and the best NOx conversion can reach up to 99%. In addition, the sulfur resistance and water resistance of the Mn6Zr0.3Co0.7 catalyst were also tested. When the concentration of SO2 is 200ppm, the NOx conversion of catalyst Mn6Zr0.3Co0.7 is still above 90%. 5 Vol% H2O has little effect on catalyst NOx conversion. The results showed that the Mn6Zr0.3Co0.7 catalyst has excellent resistance to sulfur and water. Meanwhile, the catalyst was systematically characterized. The results showed that the addition of zirconium and cobalt changes the surface morphology of the catalyst. The specific surface area, pore size, and volume of the catalyst were increased, and the reduction temperature of the catalyst was decreased. In conclusion, the doping of zirconium and cobalt successfully improves the NH3-SCR activity of the catalyst.

Promoting effect of Fe/La loading on γ-Al2O3 catalyst for hydrolysis of carbonyl sulfur.

Catalytic hydrolysis of carbonyl sulfur (COS) from blast furnace gas is one of the keys to achieving ultra-low emission in the iron-steel industry. To improve the COS hydrolysis activity on γ-Al2O3 catalyst at low temperature, catalysts with Fe or La as the active component were prepared by the impregnation method, the physical and chemical properties of the catalyst were characterized by ICP, XRF, XRD, BET, and TPD. The hydrolysis activity of COS and sulfur resistance ability on various catalysts were investigated in a fixed bed reactor combined with gas chromatography. The results show that the addition of Fe or La improves the COS hydrolysis activity due to the increase in alkaline sites on the catalyst surface. The roles of various alkaline sites on catalysts have been recognized. The weak alkaline center is the reaction site of COS hydrolysis, the middle and strong alkaline centers are the adsorption and oxidation sites of H2S. The Fe/Al2O3 catalyst has higher hydrolytic activity and oxidative capacity for H2S removal due to forming more sulfate species on Fe. The La/Al2O3 catalyst has higher hydrolysis efficiency in that H2S rapidly desorbs from the catalyst surface to the gas phase, and then, the activity of reaction sites is recovered. This provides an idea for the preparation of sulfur-resistant catalysts.

Hexagonal MBene (Hf2BO2): A Promising Platform for the Electrocatalysis of Hydrogen Evolution Reaction.

Hexagonal MAB (h-MAB) phases and their two-dimensional (2-D) derivatives (h-MBenes) have emerged as promising materials since the discovery of Ti2InB2. Herein, we identified that a possible h-MBene, 2-D Hf2BO2, can be an excellent platform for the electrocatalysis of hydrogen evolution reaction (HER) by density functional theory calculations. We proposed two approaches of transition metal (TM) modifications by atom deposition and implanting to optimize the HER performance of 2-D Hf2BO2. It is revealed that a moderate charge reduction of surface O, which is induced by the introduction of TM atoms, is conductive to a higher catalytic performance. The synergistic effect between implanted TM atoms and Hf2BO2 matrix can efficiently activate the surface by broadening O-p orbitals and shifting up p-band center, especially for V, Cr, and Mo as dopants, which can reduce the Gibbs free energy (ΔGH*) from 0.939 to -0.04, 0.05 and -0.04 eV, respectively. Interestingly, this effect works within a local region and the activity can also be evaluated by bond length of Hf-O, in addition to ΔGH*. This work suggests that due to its excellent electrocatalysis properties, h-MBenes can open up a new area for 2-D materials and will stimulate researchers to explore the synthesis of h-MAB phases and the stripping of h-MBenes.

Metal-modified sludge-based biochar enhance catalytic capacity: Characteristics and mechanism.

The improvement of the catalytic performance of sludge-based biochar plays an important role in the catalytic application of biochar. This work aimed to use transition metals and rare earth elements (Fe, Ce, La, Al, Ti) to modify sludge and prepare modified biochar with better catalytic performance through pyrolysis. Through the Fourier transform infrared spectrometer, Raman spectrometer, and X-ray photoelectron spectroscopy, the effects of different metal modifications on the surface morphology, molecular structure, element compositions, and valence of elements of biochar were comprehensively investigated. The results showed that metal elements were successfully modified onto the surface of biochar as metal oxides. Although the highest intensity of persistent free radicals was detected in blank-biochar by electron spin resonance, the intensities of hydroxyl radicals catalyzed by modified biochars in H2O2 system were higher than that catalyzed by blank-biochar, indicating that the catalytic performance of modified biochar was mainly related to the metal oxide loaded and the defect structure on the surface of metal-modified biochar. Furthermore, in the H2O2 system, the degradation efficiencies of tetracycline catalyzed by the biochars within 4 h were 51.7% (blank-biochar), 90.7% (Fe-biochar), 69.0% (Ce-biochar), 59.9% (La-biochar), 58.0% (Al-biochar), 58.0% (Ti-biochar), respectively, suggesting that Fe-biochar not only possessed the best catalytic performance but also shortened the reaction time. This research not only provided the possibility for recycling the waste activated sludge, but also proposed a modification method to improve the catalytic performance of biochar.

Computational study of phosphate adsorption on Mg/Ca modified biochar structure in aqueous solution.

Phosphate removal in water using biochar is widely investigated. Density functional theory was used to study the adsorption of phosphate (H2PO4-) on biochar in water after metal modification. Two types of metals, Mg and Ca, were used to modify the biochar structure, and the edge and metal adsorptions of H2PO4- were investigated on the modified biochar structure. Results were analyzed from the aspects of structural stability, adsorption energy, change in dipole moment, density of electronic states, and atoms in molecules analysis. The overall effect of metal-modified biochar materials on phosphate adsorption was stronger than that of unmodified biochar materials in terms of molecular level. The stability of the metal-modified structure by adding metal was low, and adsorption was prone to occur in this situation. The Ca-modified biochar showed better phosphate adsorption than the Mg-modified structure. Metal adsorption performed better than edge adsorption, proving that the modified metal in the biochar structure played a leading role in H2PO4- adsorption. Metal adsorption was mainly caused by electrostatic attraction, and edge adsorption was mainly caused by covalent bonding.

Catalytic properties of transition metals modified nanoscale zero-valent iron for simultaneous removal of 4-chlorophenol and Cr(VI): Efficacy, descriptor and reductive mechanisms.

Since chlorophenols (CPs) and Cr(VI) are two types of common pollutants in the environment, developing an effective approach to remove these contaminants has important benefits for public health. However, few efforts have been made so far. In this study, we prepared nanoscale zero-valent iron (nZVI) and a series of bimetallic nanoparticles (transition-metal modified nZVI) to investigate their catalytic properties for the simultaneous removal of 4-chlorophenol (4-CP) and Cr(VI). While nZVI enabled a fast removal of Cr(VI), it had a poor dechlorination ability. However, effective simultaneous removal of 4-CP and Cr(VI) was achieved with the transition metal modified nZVI, especially in the Pd/Fe bimetallic system. The enhanced catalytic activity of transition metal modified nZVI was primarily attributed to the formations of numerous nano-galvanic cells and atomic hydrogen species that facilitated electron transfer in the reaction system and played a key role in triggering the C-Cl bond cleavage, respectively. According to the dechlorination ability, the transition-metal catalysts examined in this study can be divided into three groups in descending order: the first being Pd and Ni, the second including Cu and Pt, while the last consisting of Au and Ag. The catalytic hydrodechlorination activity of bimetals can be well described by the volcano curve and rationally explained by the hydrogen adsorption energies on the metals, and was severely impaired by increasing Cr(VI) concentrations. Characterization results validated the formations of Fe(III)-Cr(III) hydroxide/oxyhydroxide on the bimetals surface after reacting with 4-CP and Cr(VI). This work provides the first insight into the catalytic properties of transition-metal modified nZVI for the effective removal of combined pollutants.

Preparation of Photoactive Transition-Metal Layered Double Hydroxides (LDH) to Replace Dye-Sensitized Materials in Solar Cells.

This work highlights the use of Fe-modified MgAl-layered double hydroxides (LDHs) to replace dye and semiconductor complexes in dye-sensitized solar cells (DSSCs), forming a layered double hydroxide solar cell (LDHSC). For this purpose, a MgAl-LDH and a Fe-modified MgAl LDH were prepared. X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy were used to analyze the structural properties, morphology, and success of the Fe-modification of the synthesized LDHs. Ultraviolet-visible (UV-Vis) absorption spectroscopy was used to analyze the photoactive behavior of these LDHs and compare it to that of TiO2 and dye-sensitized TiO2. Current-voltage (I-V) solar simulation was used to determine the fill factor (FF), open circuit voltage (VOC), short circuit current (ISC), and efficiency of the LDHSCs. It was shown that the MgFeAl-LDH can act as a simultaneous photoabsorber and charge separator, effectively replacing the dye and semiconductor complex in DSSCs and yielding an efficiency of 1.56%.

Water treatment residual: A critical review of its applications on pollutant removal from stormwater runoff and future perspectives.

In recent years, many studies have been conducted on using different filter media in bioretention systems for stormwater runoff treatment. This critical review paper provides a comprehensive review on the current state of water treatment residual (WTR), a recycled material that can be used as bioretention filter media for removals of key stormwater runoff pollutants (especially phosphorus) and future perspectives with innovative modification on WTR applied for pathogen removal from stormwater runoff. This review paper comprised (i) a brief summary of the reported WTR characteristics, (ii) a thorough evaluation of WTR performance on major pollutants removal from stormwater runoff (iii) a discussion on phosphorus removal mechanisms by WTR applied in the stormwater runoff treatment, and (iv) a review of the future perspectives of WTR for pathogen removal and other potential practical application in the field of stormwater treatment. As outlined in this review, WTR in stormwater runoff treatment has yet to be fully explored. The possible enhancements, especially metal surface modification on WTR are reviewed to bring about the widespread use of WTR in stormwater reuse practices.

Role of metal modified water treatment residual on removal of Escherichia coli from stormwater runoff.

Extensive studies have been conducted on bioretention filter media applied in best management practices for stormwater runoff treatment. To date, more reported studies are focused on pollutants elimination such as suspended solids and nutrients. There has been limited research on pathogen removal from stormwater runoff. More focused studies on pathogen removal are therefore required if the intended stormwater is harvested for indirect potable use. In this study, water treatment residuals (WTR), a recycled biofilter media was surface-modified with metals to assess its potential for E. coli removal from stormwater runoff. To achieve this goal, four types of modified WTRs, prepared using iron, copper, platinum, and silver as antibacterial agents, were tested in parallel batch tests. After the cost-effectiveness evaluation among the four modified WTRs for bacterial removal, Fe2O3- and CuO-WTRs were shortlisted for further mechanism and stability studies. Stable antibacterial performances (E. coli log removal of 0.58 ±â€¯0.04 and 0.90 ±â€¯0.04, respectively) were achieved using the Fe2O3- and CuO-WTRs under intermittent synthetic and natural stormwater runoff conditions. No significant metal leaching was observed over prolonged continuous treatment. The experimental results showed the bio-adsorption onto the surface modified Fe2O3- and CuO-WTR was a key mechanism for E. coli removal followed by E. coli inactivation at solid-liquid interface caused by the antibacterial effect of metal coatings (where CuO was reported to have higher biotoxicity than Fe2O3). These findings clearly suggested the potential of CuO-modified WTR for pathogen removal in stormwater treatment practices.