Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO.

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Promotion effect of Ce and Ta co-doping on the NH3-SCR performance over V2O5/TiO2 catalyst.

NH3-SCR (SCR: Selective catalytic reduction) is an effective technology for the de-NOx process from both mobile and stationary pollution sources, and the most commonly used catalysts are the vanadia-based catalysts. An innovative V2O5-CeO2/TaTiOx catalyst for NOx removal was prepared in this study. The influences of Ce and Ta in the V2O5-CeO2/TaTiOx catalyst on the SCR performance and physicochemical properties were investigated. The V2O5-CeO2/TaTiOx catalyst not only exhibited excellent SCR activity in a wide temperature window, but also presented strong resistance to H2O and SO2 at 275 ℃. A series of characterization methods was used to study the catalysts, including H2-temperature programmed reduction, X-ray photoelectron spectroscopy, NH3-temperature programmed desorption, etc. It was discovered that a synergistic effect existed between Ce and Ta species. The introduction of Ce and Ta enlarged the specific surface area, increased the amount of acid sites and the ratio of Ce3+, (V3++V4+) and Oα, and strengthened the redox capability which were related to synergistic effect between Ce and Ta species, significantly improving the NH3-SCR activity.

Review of Core-shell structure zeolite-based catalysts for NOx emission control.

Nitrogen oxides (NOx) from diesel engine exhaust, is one of the major sources of environmental pollution. Currently, selective catalytic reduction with ammonia (NH3-SCR) is considered to be the most effective protocol for reducing NOx emissions. Nowadays, zeolite-based NH3-SCR catalysts have been industrialized and widespread used in this field. Nevertheless, with the increasingly stringent environmental regulations and implementation of the requirement of "zero emission" of diesel engine exhaust, it is extremely urgent to prepare catalysts with superior NH3-SCR activity and exceptional resistance to poisons (SO2, alkali metals, hydrocarbons, etc.). Core-shell structure zeolite-based catalysts (CSCs) have shown great promise in NH3-SCR of NOx in recent years by virtue of its relatively higher low-temperature activity, broader operation temperature window and outstanding resistance to poisons. This review mainly focuses on the recent progress of CSCs for NH3-SCR of NOx with three extensively investigated SSZ-13, ZSM-5, Beta zeolites as cores. The reaction mechanisms of resistance to sulfur poisoning, alkali metal poisoning, hydrocarbon poisoning, and hydrothermal aging are summarized. Moreover, the important role of interfacial effect between core and shell in the reaction of NH3-SCR was clarified. Finally, the future development and application outlook of CSCs are prospected.

A comprehensive review of deactivation and modification of selective catalytic reaction catalysts installed in cement kilns.

After the ultralow emission transformation of coal-fired power plants, cement production became China's leading industrial emission source of nitrogen oxides. Flue gas dust contents at the outlet of cement kiln preheaters were as high as 80-100 g/m3, and the calcium oxide content in the dust exceeded 60%. Commercial V2O5(-WO3)/TiO2 catalysts suitable for coal-fired flue gas suffer from alkaline earth metal Ca poisoning of cement kiln flue gas. Recent studies have also identified the poisoning of cement kiln selective catalytic reaction (SCR) catalysts by the heavy metals lead and thallium. Investigation of the poisoning process is the primary basis for analyzing the catalytic lifetime. This review summarizes and analyzes the SCR catalytic mechanism and chronicles the research progress concerning this poisoning mechanism. Based on the catalytic and toxification mechanisms, it can be inferred that improving the anti-poisoning performance of a catalyst enhances its acidity, surface redox performance-active catalytic sites, and shell layer protection. The data provide support in guiding engineering practice and reducing operating costs of SCR plants. Finally, future research directions for SCR denitrification catalysts in the cement industry are discussed. This study provides critical support for the development and optimization of poisoning-resistant SCR denitrification catalysts.

Construction of dual sites on FeS2 surface for enhanced electrocatalytic reduction of nitrite to ammonia.

Cost-effective iron sulfides (FeS2) hold great potential as high-performance catalysts for NO2- electroreduction to NH3 (NO2ER), which is hindered by the weak NO2 activation. Herein, the design of nonmetal-doped FeS2 electrocatalysts was initially conducted by density functional theory (DFT) computations. We found that doping with different nonmetal atoms effectively not only regulates the electronic structures of the d-electrons of Fe atoms but also creates the unique p-d hybridized dual active sites, thereby boosting the efficient NO2 activation. Owing to the optimal NO2 adsorption strength, N-doped FeS2 demonstrates a low limiting potential for the NO2--to-NH3 conversion, thus significantly improving NO2ER activity. Direct experimental evidence was provided afterward: an NH3 yield rate of 424.5 µmol/hcm-2 with a 92.4 % Faradaic efficiency was achieved. Our findings not only suggest a promising NO2ER catalyst through theoretical computations to guide experiments but also provide a comprehensive understanding of the structure-properties relationship.

Stabilizing Hydrogen Radicals in Two-Dimensional Cobalt-Copper Mesoporous Nanoplates for Complete Nitrate Reduction Electrocatalysis to Ammonia.

Ambient electrochemical reduction of waste nitrate (NO3-) represents an alternative green route for sustainable ammonia (NH3) electrosynthesis in water. Despites some encouraged achievements, sluggish eight electron and nine proton reduction routes that involve multi-step hydrogenation pathways have severely hindered their NH3 Faradaic efficiency (FENH3) and yield rate. Herein, we develop a robust two-dimensional mesoporous cobalt-copper (meso-CoCu) nanoplate electrocatalyst that delivers excellent performance of complete NO3- reduction reaction (NO3RR), including superior FENH3 of 98.8%, high NH3 yield rate of 3.39 mol h-1 g-1 and energy efficiency of 49.8%, and good cycling stability. Mechanism investigations unveil that active hydrogen (*H) radicals produced from water splitting on Co sites spillover to adjacent Cu sites and further stabilize within confined mesopores, which kinetically promote its coupling hydrogenation reactions of nitrogen intermediates and thus facilitate complete NO3RR for favorable NH3 electrosynthesis. Moreover, meso-CoCu nanoplates perform well as a bifunctional electrocatalyst in the two-electrode coupling system that concurrently synthesizes NH3 from NO3- at cathode and 2,5-furanedicarboxylic acid from 5-hydroxymethylfurfural at anode. This work in stabilizing *H radicals in mesoporous microenvironment provides some insights applied to various hydrogenation reactions for selective electrosynthesis of highly value-added chemicals in water.

Efficient strategy for employing HN-AD bacterium enhanced biofilter reactors to remove NH3 and reduce secondary pollution.

Heterotrophic nitrification-aerobic denitrification (HN-AD) strain (Paracoccus denitrificans HY-1) was employed in this study to enhance the removal efficiency of NH3 in a biological trickling filter (BTF) reactor. The results demonstrated that inoculation with HY-1 and packed with bamboo charcoal as filler significantly improved the RE of NH3 in BTF, reaching 96.52 % under 27 s of empty bed residence time (EBRT) and 812.56 ppm of inlet gas concentration. Meanwhile, the titer of NH4+-N, NO2--N, and NO3--N in the circulating fluid were merely 8.52 mg/L, 5.14 mg/L, and 18.07 mg/L, respectively. Microbial community and metabolism analyses revealed that HY-1 have successfully colonized in the BTF, and the high expression of denitrification-related genes (nar, nap, nir, nor and nos) further confirmed that the inoculation of HY-1 greatly improved both nitrification and denitrification metabolism. Furthermore, the biofilter reactor inoculated with HY-1 was applied at a large-scale piggery and exhibited remarkable odor removal effect, in which 99.61 % of NH3 and 96.63 % of H2S were completely eliminated. In general, the HN-AD bacterium could strengthen the performance of BTF reactor and reduce the secondary pollution of circulating fluid during bio-deodorization.

Regulating RuxMoy Nanoalloys Anchored on Porous Nitrogen-Doped Carbon via Domain-Confined Etching Strategy for Neutral Efficient Ammonia Electrosynthesis.

Neutral electrochemical nitrate (NO3-) reduction to ammonia involves sluggish and complex kinetics, so developing efficient electrocatalysts at low potential remains challenging. Here, we report a domain-confined etching strategy to construct RuxMoy nanoalloys on porous nitrogen-doped carbon by optimizing the Ru-to-Mo ratio, achieving efficient neutral NH3 electrosynthesis. Combining in situ spectroscopy and theoretical simulations demonstrated a rational synergic effect between Ru and Mo in nanoalloys that reinforces *H adsorption and lowers the energy barrier of NO3- hydrodeoxygenation for NH3 production. The resultant Ru5Mo5-NC surpasses 92.8% for NH3 selectivity at the potential range from -0.25 to -0.45 V vs RHE under neutral electrolyte, particularly achieving a high NH3 selectivity of 98.3% and a corresponding yield rate of 1.3 mg h-1 mgcat-1 at -0.4 V vs RHE. This work provides a synergic strategy that sheds light on a new avenue for developing efficient multicomponent heterogeneous catalysts.

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.

High-Yield WS2 Synthesis through Sulfurization in Custom-Modified Atmospheric Pressure Chemical Vapor Deposition Reactor, Paving the Way for Selective NH3 Vapor Detection.

Nanostructured transition metal dichalcogenides have garnered significant research interest for physical and chemical sensing applications due to their unique crystal structure and large effective surface area. However, the high-yield synthesis of these materials on different substrates and in nanostructured films remains a challenge that hinders their real-world applications. In this work, we demonstrate the synthesis of two-dimensional (2D) tungsten disulfide (WS2) sheets on a hundred-milligram scale by sulfurization of tungsten trioxide (WO3) powder in an atmospheric pressure chemical vapor deposition reactor. The as-synthesized WS2 powders can be formulated into inks and deposited on a broad range of substrates using techniques like screen or inkjet printing, spin-coating, drop-casting, or airbrushing. Structural, morphological, and chemical composition analysis confirm the successful synthesis of edge-enriched WS2 sheets. The sensing performance of the WS2 films prepared with the synthesized 2D material was evaluated for ammonia (NH3) detection at different operating temperatures. The results reveal exceptional gas sensing responses, with the sensors showing a 100% response toward 5 ppm of NH3 at 150 °C. The sensor detection limit was experimentally verified to be below 1 ppm of NH3 at 150 °C. Selectivity tests demonstrated the high selectivity of the edge-enriched WS2 films toward NH3 in the presence of interfering gases like CO, benzene, H2, and NO2. Furthermore, the sensors displayed remarkable stability against high levels of humidity, with only a slight decrease in response from 100% in dry air to 93% in humid environments. Density functional theory and Bayesian optimization simulations were performed, and the theoretical results agree with the experimental findings, revealing that the interaction between gas molecules and WS2 is primarily based on physisorption.

Removal and recovery of nitrogen from anaerobically treated leachate based on a neglected HNAD nitrogen removal pathway: NH3 stripping.

The heterotrophic nitrification aerobic denitrification (HNAD) process can withstand the environment with high NH4+-N concentration and complex components, and has the potential to be an effective scheme for nitrogen removal of anaerobically treated leachate from municipal solid waste incineration plant. But its mechanism is still unclear and the NH3 stripping process has received little attention. At the same time, the high concentration of NH4+-N in the anaerobically treated leachate also has great recycling potential. In this study, typical HNAD microorganisms were enriched and used for nitrogen removal from anaerobically treated leachate. A one-step system with a total nitrogen removal ratio of more than 98 % was constructed. Isotopic labeling experiments showed that nitrogen was not the main product. The important role of NH3 stripping in the HNAD system was defined, and 46.63 % nitrogen was recovered on this basis.

Photoelectrocatalytic-Microbial Biohybrid for Nitrogen Reduction.

Nitrogen (N2) conversion to ammonia (NH3) in a mild condition is a big chemical challenge. The whole-cell diazotrophs based biological NH3 synthesis is one of the most promising strategies. Herein, the first attempt of photoelectrochemical-microbial (PEC-MB) biohybrid is contributed for artificial N2 fixation, where Azotobacter vinelandii (A. vinelandii) is interfaced directly with polydopamine encapsulated nickel oxide (NiO) nanosheets (NiO@PDA). By virtue of excellent bio-adhesive activity, high conductivity, and good biocompatibility of PDA layer, abundant A. vinelandii are effectively adsorbed on NiO@PDA to form NiO@PDA/A. vinelandii biohybrid, and the rationally designed biohybrid achieved a record-high NH3 production yield of 1.85 µmol h-1/108 cells (4.14 µmol h-1 cm-2). In addition, this biohybrid can operate both under illumination with a PEC model or in dark with an electrocatalytic (EC) model to implement long-term and successional NH3 synthesis. The enhancement mechanism of NH3 synthesis in NiO@PDA/A. vinelandii biohybrid can be ascribed to the increase of nicotinamide adenine dinucleotide-hydrogen (NADH) and adenosine 5-triphosphate (ATP) concentrations and over expression of nitrogen-fixing genes of nifH, nifD and nifK in nitrogenase. This innovative PEC-MB biohybrid strategy sheds light on the fundamental mechanism and establishes proof of concept of biotic-abiotic photosynthetic systems for sustainable chemical production.

Water-Driven Surface Lattice Oxygen Activation in MnO2 for Promoted Low-Temperature NH3-SCR.

Water is ubiquitous in various heterogeneous catalytic reactions, where it can be easily adsorbed, chemically dissociated, and diffused on catalyst surfaces, inevitably influencing the catalytic process. However, the specific role of water in these reactions remains unclear. In this study, we innovatively propose that H2O-driven surface lattice oxygen activation in γ-MnO2 significantly enhances low-temperature NH3-SCR. The proton from water dissociation activates the surface lattice oxygen in γ-MnO2, giving rise to a doubling of catalytic activity (achieving 90% NO conversion at 100 °C) and remarkable stability. Comprehensive in situ characterizations and calculations reveal that spontaneous proton diffusion to the surface lattice oxygen reduces the orbital overlap between the protonated oxygen atom and its neighboring Mn atom. Consequently, the Mn-O bond is weakened and the surface lattice oxygen is effectively activated to provide excess oxygen vacancies available for converting O2 into O2-. Therefore, the redox property of Mn-H is improved, leading to enhanced NH3 oxidation-dehydrogenation and NO oxidation processes, which are crucial for low-temperature NH3-SCR. This work provides a deeper understanding and fresh perspectives on the water promotion mechanism in low-temperature NOx elimination.

Ammonia-sensitive halide CsCu2I3 film for gas sensor and stimuli-responsive anti-counterfeiting.

Eco-friendly lead-free halide perovskites have emerged as promising materials for multiple applications due to their unique optoelectronic properties. In this work, we investigate the ammonia (NH3)-sensitive CsCu2I3 film for its potential in NH3 sensor and stimuli-responsive fluorescence anti-counterfeiting. CsCu2I3-based NH3 sensor demonstrates a high response to NH3 (△R/R0 = 1.07, at 100 ppm NH3) with rapid response/recovery time (21/19 s), as well as favorable gas selectivity. We proposed a potential NH3 sensing mechanism with the help of a series of semi-quantitative characterizations and excitation-dependent emission experiments. The electron-donating NH3 molecules can efficiently donate electrons to the p-type CsCu2I3 film, bringing about a decrease in film conductivity. Additionally, the adsorption of NH3 can also disorder the CsCu2I3 crystals with a high density of trap states, facilitating an energy transfer from self-trapped excitons (STEs) emission to defect-related emission, along with bright orange luminescence. Inspired by this phenomenon, we proposed a novel application of NH3-induced stimuli-responsive fluorescence for anti-counterfeiting. The results highlight the potential of CsCu2I3 for effective dual-function applications in gas sensors and gas-triggered anti-counterfeiting.

[Role of Ammonia in Aerosol Liquid Water, pH, and Secondary Inorganic Aerosols Formation at an Ammonia-rich City in Changzhou].

Ammonia （NH3） is an important alkaline reactive nitrogen, which, as a precursor of fine particulate matter, raises public health issues. In this study, online NH3, SO2, NO2, PM2.5, and its water-soluble inorganic ions were detected to deduce the influence of NH3 on aerosol liquid water content （AWC） and aerosol pH, including the formation of water-soluble secondary ions in PM2.5 in winter in Changzhou, an ammonia-rich city in the Yangtze River Delta area in winter. The results showed that NH4+ mainly existed in the form of NH4NO3 and （NH4）2SO4, and the remaining NH4+ existed as NH4Cl. Owing to the NH3-NH4+ buffer system, the aerosol pH values were found at 4.2 ± 0.4, which was positively correlated with the NH3 content. The aerosol pH value variation narrowed with the increase in PM2.5 concentration and tended to be between 4 to 5. AWC increased exponentially with the increase in humidity and SNA content, among which NH4NO3, （NH4）2SO4, and NH4Cl contributed 58.5%, 18.4%, and 8.3%, respectively, due to their hygroscopicity. Aerosol pH, AWC, and NH3-NH4+ conversion promoted the gas-to-particle conversion of SO2 and NO2. In Changzhou, rich NH3-NH4+ were found to maintain relatively high pH values, push up AWC, and promote the heterogeneous reaction of SO2, whereas NO3- generation was dominated by a homogeneous reaction, which was accelerated by NH3. According to the simulation results, relatively noticeable changes in aerosol pH and AWC could be found by the reduction of up to 30% of NH3.

[Multi-time Scale Variation of Atmospheric Ammonia Concentration and Dry Deposition in a Paddy Rice Region in Subtropical China].

Meteorological factors and anthropogenic activities significantly affect atmospheric ammonia （NH3） concentration and its dry deposition. Former studies have examined the spatial and temporal variability in atmospheric NH3 concentrations at monthly scales. However, the characteristics of atmospheric concentrations at finer time scales such as hourly and daily scales and the influencing factors remain unclear. In this study, atmospheric NH3 concentration and related meteorological factors were continuously monitored online for one year in a double cropping rice region in subtropical China, and atmospheric NH3 concentration and its meteorological influencing factors as well as dry deposition were analyzed at different time scales （hourly, daily, and monthly）. The main results were as follows： The annual average daily concentration of NH3 in the rice area varied from 0.01 to 58.0 µg·m-3 （in N, same below）, and the annual average concentration was 5.3 µg·m-3. On the hourly scale, the 24-hour dynamics of atmospheric NH3 concentration showed a unimodal pattern, and the time of the NH3 peak appearance in different seasons was different； the time of the peak that appeared in winter lagged behind that in the other seasons. From the perspective of daily scale, NH3 concentration was mainly affected by fertilization in the paddy fields, peaking at 1-3 days after fertilization and then gradually decreasing. On the monthly scale, NH3 concentration peaked at 12.8 µg·m-3 in July and was the lowest in October at 1.6 µg·m-3. On the hourly scale, NH3 concentration varied seasonally due to the influences of meteorological factors, mainly as follows： NH3 concentration showed significant positive correlations with air temperature and solar radiation in all four seasons and with wind speed in spring and summer, whereas it showed significant negative correlations with relative humidity except in winter. On the daily scale, NH3 concentration showed a significant positive correlation with air temperature, rainfall, and solar radiation, whereas it showed a significant negative correlation with relative humidity. On the monthly scale, no significant correlation existed between each meteorological factor and NH3 concentration. The annual dry deposition flux （in N） calculated from the hourly average NH3 concentration was 8.5 kg·ï¼ˆhm2·a）-1, which was 11.6% higher than the annual flux calculated from the daily average and 12.4% higher than the annual flux calculated from the monthly average. In summary, there were significant daily and seasonal variations in atmospheric NH3 concentration in the paddy rice region in subtropical China, and conducting hourly-scale observations of NH3 concentration can help to reveal the multi-time scale variations in NH3 concentration and to quantify NH3 dry deposition more accurately.

Preparation and characterisation of NH3 gas sensor based on PANI/Fe-doped CeO 2 nanocomposite.

PANI/Fe-doped CeO 2 nanocomposite was synthesised by the in-situ process. The produced powders were characterised by XRD, XPS, FT-IR, Raman, HRTEM and SEM-EDS tests. The sensors' function was based on PANI/Fe-doped CeO 2 nanocomposite with thin film deposited on top of interdigitated electrodes (IDT). NH 3 detection with PANI/Fe-doped CeO 2 nanocomposite sensor could be successfully performed even at room temperature (RT) and relative humidity of 45 %. Results demonstrated that PANI/Fe-doped CeO 2 might be promising sensing materials for detecting the low NH 3 concentration (ppm). In addition, the sensor is selective to the interfering gases, including CO, CO 2 and NO 2 . This sensor displays acceptable repeatability and stability over time.

Cu Nanowires Encapsulated by ZIF67 for Efficient Ammonia Electrosynthesis from Nitrate.

Electrochemical NO3- reduction reaction (NO3RR) represents a green and sustainable way to produce valuable NH3 for both NH3 production and nitrate contaminant removal, and developing efficient, durable, highly selective catalyst is the key. Herein, we report a facile method to fabricate a catalyst composed of ultrafine Cu nanowires (Cu NWs) encapsulated by ZIF67, namely, CuNW@ZIF67, for efficient NH3 electrosynthesis from nitrate. The CuNW@ZIF67 catalyst exhibited excellent catalytic performance toward NO3RR in alkaline electrolyte, manifested by a large NH3 Faradaic efficiency of 93.7% at -0.5 V versus reversible hydrogen electrode (RHE), a high energy efficiency over 30% at -0.7 V, and robust long-term stability. Such intriguing catalytic properties are mainly ascribed to its structural merits and the strong electronic interaction between Cu NWs and ZIF67. DFT calculations revealed that, the Cu site can easily convert NO3- into NO2-, while the Co site plays a critical role in catalyzing the NO2--to-NH3 process. The study can shed light on rational design of efficient, durable, and highly selective catalysts for NO3RR and beyond.

A multi-stimuli-responsive fluorescence material based on 1,8-naphthalimide.

A pair of 1,8-naphthalimides (NPIs) were designed and successfully synthesized through embellishing amino-containing NPI with 4-diethylaminosalicyladehyde and 4-diethylaminobenzaldehyde, respectively. Their structures were fully confirmed by 1H/13C NMR, HR-MS and FT-IR spectroscopic studies. Their photophysical properties were systematically investigated in different solvents of varied polarity, in THF/water mixtures with varying water fractions (fw), and in THF solvent with varying concentrations of NPIs. It inferred that the distinct differences in emission between two NPIs during self-assembled process could be ascribed that the hydroxyl-containing NPI allowed the excited-state intramolecular proton transfer process between -OH and CH=N units in the aggregation state. Interestingly, the solid of 4-diethylaminosalicyladehyde-functionalized NPI exhibited multi-stimuli-responsive fluorescence changes involving mechanofluorochromism and HCl/NH3 vapor stimulus-induced conversion. However, no remarkable change was observed in the photoluminescence (PL) spectra for the solid of 4-diethylaminobenzaldehyde-functionalized NPI under the stimuli of mechanical force and organic solvent.

Amorphizing MnIn2S4 Atomic Layers Create an Asymmetrical InO1S5 Polarization Plane for Photocatalytic Ammonia Synthesis and CO2 Reduction.

Building a polarization center is an effective avenue to boost charge separation and molecular activation in photocatalysis. However, a limited number of polarization centers are usually created. Here, a polarization plane based on two-dimensional (2D) atomic layers is designed to maximize the surface polarization centers. The Mn in a 2D crystal lattice is etched from the MnIn2S4 atomic layers to build a consecutive symmetry-breaking structure of isolated InO1S5 sites. More charges aggregate around O, making the isolated InO1S5 sites highly polarized. Due to the formation of the InO1S5 polarization plane, an enormous polarized electric field is formed perpendicular to the 2D atomic layers and the carrier lifetime can be prolonged from 93.2 ps in MnIn2S4 to 1130 ps in amorphous MnxIn2Sy. Meantime, the formed large charge density gradient favors coupling and activation of small molecules. Benefiting from these features, a good NH3 photosynthesis performance (515.8 µmol g-1 h-1) can be realized over amorphous MnxIn2Sy, roughly 2.5 and 48.9 times higher than those of MnIn2S4 atomic layers and bulk MnIn2S4, respectively. The apparent quantum yields reach 5.4 and 3.3% at 380 and 400 nm, respectively. Meanwhile, a greatly improved CO2 reduction activity is also achieved over MnxIn2Sy. This strategy provides an accessible pathway for designing an asymmetrical polarization plane to motivate photocatalysis optimization.