Promoting C-F bond activation via proton donor for CF4 decomposition.

Tetrafluoromethane (CF4), the simplest perfluorocarbons, is a permanently potent greenhouse gas due to its powerful infrared radiation adsorption capacity. The highly symmetric and robust C-F bond structure makes its activation a great challenge. Herein, we presented an innovated approach that efficiently activates C-F bond utilizing protonated sulfate (-HSO4) modified Al2O3@ZrO2 (S-Al2O3@ZrO2) catalyst, resulting in highly efficient CF4 decomposition. By combining in situ infrared spectroscopy tests and density function theory simulations, we demonstrate that the introduced -HSO4 proton donor has a stronger interaction on the C-F bond than the hydroxyl (-OH) proton donor, which can effectively stretch the C-F bond for its activation. Consequently, the obtained S-Al2O3@ZrO2 catalyst achieved a stable 100% CF4 decomposition at a record low temperature of 580 °C with a turnover frequency value of ~8.3 times higher than the Al2O3@ZrO2 catalyst without -HSO4 modification, outperforming the previously reported results. This work paves a new way for achieving efficient C-F bond activation to decompose CF4 at a low temperature.

Tunable Surface Wettability via Terahertz Electrowave Controlled Vicinal Subnanoscale Water Layer.

Achieving timely, reversible, and long-range remote tunability over surface wettability is highly demanded across diverse fields, including nanofluidic systems, drug delivery, and heterogeneous catalysis. Herein, using molecular dynamic simulations, we show, for the first time, a theoretical design of electrowetting to achieve remotely controllable surface wettability via using a terahertz wave. The key idea driving the design is the unique terahertz collective vibration identified in the vicinal subnanoscale water layer, which is absent in bulk water, enabling efficient energy transfer from the terahertz wave to the rotational motion of the vicinal subnanoscale water layer. Consequently, a frequency-specific alternating terahertz electric field near the critical strength can significantly affect the local hydrogen-bonding network of the contact water layer on the solid surface, thereby achieving tunable surface wettability.

Synergistic Catalytic Removal of NOx and n-Butylamine via Spatially Separated Cooperative Sites.

Synergistic control of nitrogen oxides (NOx) and nitrogen-containing volatile organic compounds (NVOCs) from industrial furnaces is necessary. Generally, the elimination of n-butylamine (n-B), a typical pollutant of NVOCs, requires a catalyst with sufficient redox ability. This process induces the production of nitrogen-containing byproducts (NO, NO2, N2O), leading to lower N2 selectivity of NH3 selective catalytic reduction of NOx (NH3-SCR). Here, synergistic catalytic removal of NOx and n-B via spatially separated cooperative sites was originally demonstrated. Specifically, titania nanotubes supported CuOx-CeO2 (CuCe-TiO2 NTs) catalysts with spatially separated cooperative sites were creatively developed, which showed a broader active temperature window from 180 to 340 °C, with over 90% NOx conversion, 85% n-B conversion, and 90% N2 selectivity. A synergistic effect of the Cu and Ce sites was found. The catalytic oxidation of n-B mainly occurred at the Cu sites inside the tube, which ensured the regular occurrence of the NH3-SCR reaction on the outer Ce sites under the matching temperature window. In addition, the n-B oxidation would produce abundant intermediate NH2*, which could act as an extra reductant to promote NH3-SCR. Meanwhile, NH3-SCR could simultaneously remove the possible NOx byproducts of n-B decomposition. This novel strategy of constructing cooperative sites provides a distinct pathway for promoting the synergistic removal of n-B and NOx.

Phosphotungstic Acid as a Dechlorination Agent Collaborates with CeO2 for Synergistic Catalytic Elimination of NOx and Chlorobenzene.

The development of efficient technologies for the synergistic catalytic elimination of NOx and chlorinated volatile organic compounds (CVOCs) remains challenging. Chlorine species from CVOCs are prone to catalyst poisoning, which increases the degradation temperature of CVOCs and fails to balance the selective catalytic reduction of NOx with the NH3 (NH3-SCR) performance. Herein, synergistic catalytic elimination of NOx and chlorobenzene has been originally demonstrated by using phosphotungstic acid (HPW) as a dechlorination agent to collaborate with CeO2. The conversion of chlorobenzene was over 80% at 270 °C, and the NOx conversion and N2 selectivity reached over 95% at 270-420 °C. HPW not only allowed chlorine species to leave as inorganic chlorine but also enhanced the BroÌ·nsted acidity of CeO2. The NH4+ produced in the NH3-SCR process can effectively promote the dechlorination of chlorobenzene at low temperatures. HPW remained structurally stable in the synergistic reaction, resulting in good water resistance and long-term stability. This work provides a cheaper and more environmentally friendly strategy to address chlorine poisoning in the synergistic reaction and offers new guidance for multipollutant control.

Triggering High Capacity and Superior Reversibility of Manganese Oxides Cathode via Magnesium Modulation for Zn//MnO2 Batteries.

Aqueous zinc-ion batteries (ZIBs) have attracted extensive attention in recent years because of its high volumetric energy density, the abundance of zinc resources, and safety. However, ZIBs still suffer from poor reversibility and sluggish kinetics derived from the unstable cathodic structure and the strong electrostatic interactions between bivalent Zn2+ and cathodes. Herein, magnesium doping into layered manganese dioxide (Mg-MnO2 ) via a simple hydrothermal method as cathode materials for ZIBs is proposed. The interconnected nanoflakes of Mg-MnO2 possess a larger specific surface area compared to pristine δ-MnO2 , providing more electroactive sites and boosting the capacity of batteries. The ion diffusion coefficients of Mg-MnO2 can be enhanced due to the improved electrical conductivity by doped cations and oxygen vacancies in MnO2 lattices. The assembled Zn//Mg-MnO2 battery delivers a high specific capacity of 370 mAh g-1 at a current density of 0.6 A g-1 . Furthermore, the reaction mechanism confirms that Zn2+ insertion occurred after a few cycles of activation reactions. Most important, the reversible redox reaction between Zn2+ and MnOOH is found after several charge-discharge processes, promoting capacity and stability. It believes that this systematic research enlightens the design of high-performance of ZIBs and facilitates the practical application of Zn//MnO2 batteries.

Improved N2 Selectivity of MnOx Catalysts for NOx Reduction by Engineering Bridged Mn3+ Sites.

Mn-based catalysts are promising for selective catalytic reduction (SCR) of NOx with NH3 at low temperatures due to their excellent redox capacity. However, the N2 selectivity of Mn-based catalysts is an urgent problem for practical application owing to excessive oxidizability. To solve this issue, we report a Mn-based catalyst using amorphous ZrTiOx as the support (Mn/ZrTi-A) with both excellent low-temperature NOx conversion and N2 selectivity. It is found that the amorphous structure of ZrTiOx modulates the metal-support interaction for anchoring the highly dispersed active MnOx species and constructs a uniquely bridged Mn3+ bonded with the support through oxygen linked to Ti4+ and Zr4+, respectively, which regulates the optimal oxidizability of the MnOx species. As a result, Mn/ZrTi-A is not conducive to the formation of ammonium nitrate that readily decomposes to N2O, thus further increasing N2 selectivity. This work investigates the role of an amorphous support in promoting the N2 selectivity of a manganese-based catalyst and sheds light on the design of efficient low-temperature deNOx catalysts.

Revealing the Dynamic Behavior of Active Sites on Acid-Functionalized CeO2 Catalysts for NOx Reduction.

Unraveling the dynamics of the active sites upon CeO2-based catalysts in selective catalytic reduction of nitrogen oxides by ammonia (NH3-SCR) is challenging. In this work, we prepared tungsten-acidified and sulfated CeO2 catalysts and used operando spectroscopy to reveal the dynamics of acid sites and redox sites on catalysts during NH3-SCR reaction. We found that both Lewis and Brønsted acid sites are needed to participate in the catalytic reaction. Notably, Brønsted acid sites are the main active sites after a tungsten-acidified or sulfated treatment, and the change of Brønsted acid sites significantly affects the NOx removal. Moreover, acid functionalization promotes the cerium species cycle between Ce4+ and Ce3+ for the NOx reduction. This work is critical to deeply understanding the natural properties of active sites, and it also provides new insights into the mechanism for NH3-SCR over CeO2-based catalysts.

Ultrahighly Alkali-Tolerant NOx Reduction over Self-Adaptive CePO4/FePO4 Catalysts.

Catalyst deactivation caused by alkali metal poisoning has long been a key bottleneck in the application of selective catalytic reduction of NOx with NH3 (NH3-SCR), limiting the service life of the catalyst and increasing the cost of environmental protection. Despite great efforts, continuous accumulation of alkali metal deposition makes the resistance capacity of 2 wt % K2O difficult to enhance via merely loading acid sites on the surface, resulting in rapid deactivation and frequent replacement of the NH3-SCR catalyst. To further improve the resistance of alkali metals, encapsulating alkali metals into the bulk phase could be a promising strategy. The bottleneck of 2 wt % K2O tolerance has been solved by virtue of ultrahigh potassium storage capacity in the amorphous FePO4 bulk phase. Amorphous FePO4 as a support of the NH3-SCR catalyst exhibited a self-adaptive alkali-tolerance mechanism, where potassium ions spontaneously migrated into the bulk phase of amorphous FePO4 and were anchored by PO43- with the generation of Fe2O3 at the NH3-SCR reaction temperature. This ingenious potassium storage mechanism could boost the K2O resistance capacity to 6 wt % while maintaining approximately 81% NOx conversion. Besides, amorphous FePO4 also exhibited excellent resistance to individual and coexistence of alkali (K2O and Na2O), alkali earth (CaO), and heavy metals (PbO and CdO), providing long durability for CePO4/FePO4 catalysts in flue gas with multipollutants. The cheap and accessible amorphous FePO4 paves the way for the development and implementation of poisoning-resistant NOx abatement.

Expediting Toluene Combustion by Harmonizing the Ce-O Strength over Co-Doped CeZr Oxide Catalysts.

Low-temperature catalytic degradation of volatile organic compounds (VOCs) by enhancing the activity of non-precious metal catalysts has always been the focus of attention. The mineralization of aromatic VOCs requires the participation of a large number of oxygen atoms, so the activation of oxygen species is crucial in the degradation reaction. Herein, we originally adjust the Ce-O bond strength in CeZr oxide catalysts by cobalt doping to promote the activation of oxygen species, thus improving the toluene degradation performance while maintaining high stability. Subsequent characterizations and theoretical calculations demonstrate that the weakening of the Ce-O bond strength increases the oxygen vacancy content, promotes the activation of oxygen species, and enhances the redox ability of the catalysts. This strategy also promotes the activation of toluene and accelerates the depletion of intermediate species. This study will contribute a strategy to enhance the activation ability of oxygen species in non-noble metal oxide catalysts, thereby enhancing the degradation performance of VOCs.

Boosting Ozone Catalytic Oxidation of Toluene at Room Temperature by Using Hydroxyl-Mediated MnOx/Al2O3 Catalysts.

Ozone catalytic oxidation (OZCO) has gained great interest in environmental remediation while it still faces a big challenge during the deep degradation of refractory volatile organic compounds (VOCs) at room temperature. Hydroxylation of the catalytic surface provides a new strategy for regulating the catalytic activity to boost VOC degradation. Herein, OZCO of toluene at room temperature over hydroxyl-mediated MnOx/Al2O3 catalysts was originally demonstrated. Specifically, a novel hydroxyl-mediated MnOx/Al2O3 catalyst was developed via the in situ AlOOH reconstruction method and used for toluene OZCO. The toluene degradation performance of MnOx/Al2O3 was significantly superior to those of most of the state-of-the-art catalysts, and 100% toluene was removed with an excellent mineralization rate (82.3%) and catalytic stability during OZCO. ESR and in situ DRIFTs results demonstrated that surface hydroxyl groups (HGs) greatly improved the reactive oxygen species generation, thus dramatically accelerating the benzene ring breakage and deep mineralization. Furthermore, HGs provided anchoring sites for uniformly dispersing MnOx and greatly enhanced toluene adsorption and ozone activation. This work paves a way for deep decomposition of aromatic VOCs at room temperature.

Selective Synergistic Catalytic Elimination of NOx and CH3SH via Engineering Deep Oxidation Sites against Toxic Byproducts Formation.

NOx and CH3SH as two typical air pollutants widely coexist in various energy and industrial processes; hence, it is urgent to develop highly efficient catalysts to synergistically eliminate NOx and CH3SH. However, the catalytic system for synergistically eliminating NOx and CH3SH is seldom investigated to date. Meanwhile, the deactivation effects of CH3SH on catalysts and the formation mechanism of toxic byproducts emitted from the synergistic catalytic elimination reaction are still vague. Herein, selective synergistic catalytic elimination (SSCE) of NOx and CH3SH via engineering deep oxidation sites over Cu-modified Nb-Fe composite oxides supported on TiO2 catalyst against toxic CO and HCN byproducts formation has been originally demonstrated. Various spectroscopic and microscopic characterizations demonstrate that the sufficient chemisorbed oxygen species induced by the persistent electron transfer from Nb-Fe composite oxides to copper oxides can deeply oxidize HCOOH to CO2 for avoiding highly toxic byproducts formation. This work is of significance in designing superior catalysts employed in more complex working conditions and sheds light on the progress in the SSCE of NOx and sulfur-containing volatile organic compounds.

Improving Electrocatalytic Oxygen Evolution through Local Field Distortion in Mg/Fe Dual-site Catalysts.

Transition metal single atom electrocatalysts (SACs) with metal-nitrogen-carbon (M-N-C) configuration show great potential in oxygen evolution reaction (OER), whereby the spin-dependent electrons must be allowed to transfer along reactants (OH- /H2 O, singlet spin state) and products (O2 , triplet spin state). Therefore, it is imperative to modulate the spin configuration in M-N-C to enhance the spin-sensitive OER energetics, which however remains a significant challenge. Herein, we report a local field distortion induced intermediate to low spin transition by introducing a main-group element (Mg) into the Fe-N-C architecture, and decode the underlying origin of the enhanced OER activity. We unveil that, the large ionic radii mismatch between Mg2+ and Fe2+ can cause a FeN4 in-plane square local field deformation, which triggers a favorable spin transition of Fe2+ from intermediate (dxy 2 dxz 2 dyz 1 dz2 1 , 2.96 µB ) to low spin (dxy 2 dxz 2 dyz 2 , 0.95 µB ), and consequently regulate the thermodyna-mics of the elementary step with desired Gibbs free energies. The as-obtained Mg/Fe dual-site catalyst demonstrates a superior OER activity with an overpotential of 224 mV at 10 mA cm-2 and an electrolysis voltage of only 1.542 V at 10 mA cm-2 in the overall water splitting, which outperforms those of the state-of-the-art transition metal SACs.

Atomically Local Electric Field Induced Interface Water Reorientation for Alkaline Hydrogen Evolution Reaction.

The slow water dissociation process in alkaline electrolyte severely limits the kinetics of HER. The orientation of H2 O is well known to affect the dissociation process, but H2 O orientation is hard to control because of its random distribution. Herein, an atomically asymmetric local electric field was designed by IrRu dizygotic single-atom sites (IrRu DSACs) to tune the H2 O adsorption configuration and orientation, thus optimizing its dissociation process. The electric field intensity of IrRu DSACs is over 4.00×1010  N/C. The ab initio molecular dynamics simulations combined with in situ Raman spectroscopy analysis on the adsorption behavior of H2 O show that the M-H bond length (M=active site) is shortened at the interface due to the strong local electric field gradient and the optimized water orientation promotes the dissociation process of interfacial water. This work provides a new way to explore the role of single atomic sites in alkaline hydrogen evolution reaction.

NOx Reduction over Smart Catalysts with Self-Created Targeted Antipoisoning Sites.

Selective catalytic reduction of NOx in the presence of alkali (earth) metals and heavy metals is still a challenge due to the easy deactivation of catalysts. Herein, NOx reduction over smart catalysts with self-created targeted antipoisoning sites is originally demonstrated. The smart catalyst consisted of TiO2 pillared montmorillonite with abundant cation exchange sites to anchor poisoning substances and active components to catalyze NOx into N2. It was not deactivated during the NOx reduction process in the presence of alkali (earth) metals and heavy metals. The enhanced surface acidity, reducible active species, and active chemisorbed oxygen species of the smart catalyst accounted for the remarkable NOx reduction efficiency. More importantly, the self-created targeted antipoisoning sites expressed specific anchoring effects on poisoning substances and protected the active components from poisoning. It was demonstrated that the tetrahedrally coordinated aluminum species of the smart catalyst mainly acted as self-created targeted antipoisoning sites to stabilize the poisoning substances into the interlayers of montmorillonite. This work paves a new way for efficient reduction of NOx from the complex flue gas in practical applications.

Low-Temperature Combustion of Toluene over Cu-Doped SmMn2O5 Mullite Catalysts via Creating Highly Active Cu2+-O-Mn4+ Sites.

Catalytic combustion of volatile organic compounds (VOCs) at low temperatures is still an urgent issue to be solved. Herein, low-temperature combustion of toluene over Cu-doped SmMn2O5 mullite catalysts via creating highly active Cu2+-O-Mn4+ sites has been originally demonstrated. Cu-doped SmMn2O5 mullite catalysts exhibited 90% conversion of toluene at 206 °C and displayed robust stability even in the presence of water. It has been demonstrated that Cu doping created Cu2+-O-Mn4+ active composite sites that were more exposed after removing surface Sm species via acid-etching. Benefiting from this, the redox and oxygen activation ability of catalysts was significantly enhanced. The consumption of benzaldehyde and benzoic acid as intermediate species and the CO2 generation ability were apparently promoted, which were the direct reasons for the enhanced low-temperature combustion of toluene. This work provides novel ideas for the development of high-performance catalysts for low-temperature VOC combustion, which has great industrial application prospects.

Unique Compensation Effects of Heavy Metals and Phosphorus Copoisoning over NOx Reduction Catalysts.

Selective catalytic reduction (SCR) of NOx from the flue gas is still a grand challenge due to the easy deactivation of catalysts. The copoisoning mechanisms and multipoisoning-resistant strategies for SCR catalysts in the coexistence of heavy metals and phosphorus are barely explored. Herein, we unexpectedly found unique compensation effects of heavy metals and phosphorus copoisoning over NOx reduction catalysts and the introduction of heavy metals results in a dramatic recovery of NOx reduction activity for the P-poisoned CeO2/TiO2 catalysts. P preferentially combines with Ce as a phosphate species to reduce the redox capacity and inhibit NO adsorption. Heavy metals preferentially reduced the Brønsted acid sites of the catalyst and inhibited NH3 adsorption. It has been demonstrated that heavy metal phosphate species generated over the copoisoned catalyst, which boosted the activation of NH3 and NO, subsequently bringing about more active nitrate species to relieve the severe impact by phosphorus and maintain the NOx reduction over CeO2/TiO2 catalysts. The heavy metals and P copoisoned catalysts also possessed more acidic sites, redox sites, and surface adsorbed oxygen species, which thus contributed to the highly efficient NOx reduction. This work elaborates the unique compensation effects of heavy metals and phosphorus copoisoning over CeO2/TiO2 catalysts for NOx reduction and provides a perspective for further designing multipoisoning-resistant CeO2-based catalysts to efficiently control NOx emissions in stationary sources.

Alkali and Heavy Metal Copoisoning Resistant Catalytic Reduction of NOx via Liberating Lewis Acid Sites.

The catalyst deactivation caused by the coexistence of alkali and heavy metals remains an obstacle for selective catalytic reduction of NOx with NH3. Moreover, the copoisoning mechanism of alkali and heavy metals is still unclear. Herein, the copoisoning mechanism of K and Cd was revealed from the adsorption and variation of reaction intermediates at a molecular level through time-resolved in situ spectroscopy combined with theoretical calculations. The alkali metal K mainly decreased the adsorption of NH3 on Lewis acid sites and altered the reaction more depending on the formation of the NH4NO3 intermediate, which is highly related to NOx adsorption and activation. However, Cd further inhibited the generation of active nitrate intermediates and thus decreased the NOx abatement about 60% on potassium-poisoned CeTiOx catalysts. Physically mixing with acid additives for CeTiOx catalysts could significantly liberate the active Lewis acid sites from the occupation of alkali metals and relieve the high dependence on NOx adsorption and activation, thus recovering the NOx removal rate to the initial state. This work revealed the copoisoning mechanism of K and Cd on Ce-based de-NOx catalysts and developed a facile anti-poisoning strategy, which paves a way for the development of durable catalysts among alkali and heavy metal copoisoning resistant catalytic reduction of NOx.

SO2- and H2O-Tolerant Catalytic Reduction of NOx at a Low Temperature via Engineering Polymeric VOx Species by CeO2.

Selective catalytic reduction (SCR) of NOx over V2O5-based oxide catalysts has been widely used, but it is still a challenge to efficiently reduce NOx at low temperatures under SO2 and H2O co-existence. Herein, SO2- and H2O-tolerant catalytic reduction of NOx at a low temperature has been originally demonstrated via engineering polymeric VOx species by CeO2. The polymeric VOx species were tactfully engineered on Ce-V2O5 composite active sites via the surface occupation effect of Ce, and the obtained catalysts exhibited remarkable low-temperature activity and strong SO2 and H2O tolerance at 250 °C. The strong interaction between Ce and V species induced the electron transfer from V to Ce and tuned the SCR reaction via the E-R pathway between the NH4+/NH3 species and gaseous NO. In the presence of SO2 and H2O, the polymeric VOx species had not been hardly influenced, while the formation of sulfate species on Ce sites not only promoted the adsorption of NH4+ species and the reaction between gaseous NO and NH4+ but also facilitated the decomposition of ammonium bisulfate through weakening the strong bond between HSO4- and NH4+. This work provided a new strategy for SO2- and H2O-tolerant catalytic reduction of NOx at a low temperature.

SO2-Tolerant Catalytic Reduction of NOx via Tailoring Electron Transfer between Surface Iron Sulfate and Subsurface Ceria.

Currently, SO2-induced catalyst deactivation from the sulfation of active sites turns to be an intractable issue for selective catalytic reduction (SCR) of NOx with NH3 at low temperatures. Herein, SO2-tolerant NOx reduction has been originally demonstrated via tailoring the electron transfer between surface iron sulfate and subsurface ceria. Engineered from the atomic layer deposition followed by the pre-sulfation method, the structure of surface iron sulfate and subsurface ceria was successfully constructed on CeO2/TiO2 catalysts, which delivered improved SO2 resistance for NOx reduction at 250 °C. It was demonstrated that the surface iron sulfate inhibited the sulfation of subsurface Ce species, while the electron transfer from the surface Fe species to the subsurface Ce species was well retained. Such an innovative structure of surface iron sulfate and subsurface ceria notably improved the reactivity of NHx species, thus endowing the catalysts with a high NOx reaction efficiency in the presence of SO2. This work unraveled the specific structure effect of surface iron sulfate and subsurface ceria on SO2-toleant NOx reduction and supplied a new point to design SO2-tolerant catalysts by modulating the unique electron transfer between surface sulfate species and subsurface oxides.

Self-Defense Effects of Ti-Modified Attapulgite for Alkali-Resistant NOx Catalytic Reduction.

Nowadays, the serious deactivation of deNOx catalysts caused by alkali metal poisoning was still a huge bottleneck in the practical application of selective catalytic reduction of NOx with NH3. Herein, alkali-resistant NOx catalytic reduction over metal oxide catalysts using Ti-modified attapulgite (ATP) as supports has been originally demonstrated. The self-defense effects of Ti-modified ATP for alkali-resistant NOx catalytic reduction have been clarified. Ti-modified ATP with self-defense ability was obtained by removing alkaline metal cation impurities in the natural ATP materials without destroying its initial layered-chain structure through the ion-exchange procedure, accompanied with an obvious enrichment of Brønsted acid and Lewis acid sites. The self-defense effects embodied that both ion-exchanged Ti octahedral centers and abundant Si-OH sites in the Ti-ion-exchange-modified ATP could effectively anchor alkali metals via coordinate bonding or ion-exchange process, which induced alkali metals to be immobilized by the Ti-ion-exchange-modified ATP carrier rather than impair active species. Under this special protection of self-defense effects, Ti-ion-exchange-modified ATP supported catalysts still retained plentiful acidic sites and superior redox ability even after alkali metal poisoning, giving rise to the maintenance of sufficient NHx and NOx adsorption and the subsequent efficient reaction, which in turn resulted in high NOx catalytic reduction capacity of the catalyst. The strategy provided new inspiration for the development of novel and efficient selective catalytic reduction of NOx with NH3 (NH3-SCR) catalysts with high alkali resistance.