Pathways of N2O production by marine ammonia-oxidizing archaea determined from dual-isotope labeling.

The ocean is a net source of the greenhouse gas and ozone-depleting substance, nitrous oxide (N2O), to the atmosphere. Most of that N2O is produced as a trace side product during ammonia oxidation, primarily by ammonia-oxidizing archaea (AOA), which numerically dominate the ammonia-oxidizing community in most marine environments. The pathways to N2O production and their kinetics, however, are not completely understood. Here, we use 15N and 18O isotopes to determine the kinetics of N2O production and trace the source of nitrogen (N) and oxygen (O) atoms in N2O produced by a model marine AOA species, Nitrosopumilus maritimus. We find that during ammonia oxidation, the apparent half saturation constants of nitrite and N2O production are comparable, suggesting that both processes are enzymatically controlled and tightly coupled at low ammonia concentrations. The constituent atoms in N2O are derived from ammonia, nitrite, O2, and H2O via multiple pathways. Ammonia is the primary source of N atoms in N2O, but its contribution varies with ammonia to nitrite ratio. The ratio of 45N2O to 46N2O (i.e., single or double labeled N) varies with substrate ratio, leading to widely varying isotopic signatures in the N2O pool. O2 is the primary source for O atoms. In addition to the previously demonstrated hybrid formation pathway, we found a substantial contribution by hydroxylamine oxidation, while nitrite reduction is an insignificant source of N2O. Our study highlights the power of dual 15N-18O isotope labeling to disentangle N2O production pathways in microbes, with implications for interpretation of pathways and regulation of marine N2O sources.

Resolving the amine-promoted hydrolysis mechanism of N2O5 under tropospheric conditions.

Hydrolysis of N2O5 under tropospheric conditions plays a critical role in assessing the fate of O3, OH, and NOx in the atmosphere. However, its removal mechanism has not been fully understood, and little is known about the role of entropy. Herein, we propose a removal path of N2O5 on the water clusters/droplet with the existence of amine, which entails a low free-energy barrier of 4.46 and 3.76 kcal/mol on a water trimer and droplet, respectively, at room temperature. The free-energy barrier exhibits strong temperature dependence; a barrierless hydrolysis process of N2O5 at low temperature (≤150 K) is observed. By coupling constrained ab initio molecular dynamics (constrained AIMD) simulations with thermodynamic integration methods, we quantitively evaluated the entropic contributions to the free energy and compared NH3-, methylamine (MA)-, and dimethylamine (DMA)-promoted hydrolysis of N2O5 on water clusters and droplet. Our results demonstrate that methylation of NH3 stabilizes the product state and promotes hydrolysis of N2O5 by reducing the free-energy barriers. Furthermore, a quantitative analysis of the internal coordinate distribution of the reaction center and the relative position of surrounding species reveals that the significant entropic contribution primarily results from the ensemble effect of configurations observed in the AIMD simulations. Such an ensemble effect becomes more significant with more water molecules included. Lowering the temperature effectively minimizes the entropic contribution, making the hydrolysis more exothermic and barrierless. This study sheds light on the importance of the promoting effect of amines and the entropic effect on gas-phase hydrolysis reactions, which may have far-reaching implications in atmospheric chemistry.

A gap in nitrous oxide emission reporting complicates long-term climate mitigation.

Nitrous oxide (N2O) is an important greenhouse gas (GHG) that also contributes to depletion of ozone in the stratosphere. Agricultural soils account for about 60% of anthropogenic N2O emissions. Most national GHG reporting to the United Nations Framework Convention on Climate Change assumes nitrogen (N) additions drive emissions during the growing season, but soil freezing and thawing during spring is also an important driver in cold climates. We show that both atmospheric inversions and newly implemented bottom-up modeling approaches exhibit large N2O pulses in the northcentral region of the United States during early spring and this increases annual N2O emissions from croplands and grasslands reported in the national GHG inventory by 6 to 16%. Considering this, emission accounting in cold climate regions is very likely underestimated in most national reporting frameworks. Current commitments related to the Paris Agreement and COP26 emphasize reductions of carbon compounds. Assuming these targets are met, the importance of accurately accounting and mitigating N2O increases once CO2 and CH4 are phased out. Hence, the N2O emission underestimate introduces additional risks into meeting long-term climate goals.

Direct Eight-Electron N2O Electroreduction to NH3 Enabled by an Fe Double-Atom Catalyst.

N2O is a dominant atmosphere pollutant, causing ozone depletion and global warming. Currently, electrochemical reduction of N2O has gained increasing attention to remove N2O, but its product is worthless N2. Here, we propose a direct eight-electron (8e) pathway to electrochemically convert N2O into NH3. As a proof of concept, using density functional theory calculation, an Fe2 double-atom catalyst (DAC) anchored by N-doped porous graphene (Fe2@NG) was screened out to be the most active and selective catalyst for N2O electroreduction toward NH3 via the novel 8e pathway, which benefits from the unique bent N2O adsorption configuration. Guided by theoretical prediction, Fe2@NG DAC was fabricated experimentally, and it can achieve a high N2O-to-NH3 Faradaic efficiency of 77.8% with a large NH3 yield rate of 2.9 mg h-1 cm-2 at -0.6 V vs RHE in a neutral electrolyte. Our study offers a feasible strategy to synthesize NH3 from pollutant N2O with simultaneous N2O removal.

Utilizing plasma-generated N2O5 gas from atmospheric air as a novel gaseous nitrogen source for plants.

Fixing atmospheric nitrogen for use as fertilizer is a crucial process in promoting plant growth and enhancing crop yields in agricultural production. Currently, the chemical production of nitrogen fertilizer from atmospheric N2 relies on the energy-intensive Haber-Bosch process. Therefore, developing a low-cost and easily applicable method for fixing nitrogen from the air would provide a beneficial alternative. In this study, we tested the utilization of dinitrogen pentoxide (N2O5) gas, generated from oxygen and nitrogen present in ambient air with the help of a portable plasma device, as a nitrogen source for the model plant Arabidopsis thaliana. Nitrogen-deficient plants supplied with medium treated with N2O5, were able to overcome nitrogen deficiency, similar to those provided with medium containing a conventional nitrogen source. However, prolonged direct exposure of plants to N2O5 gas adversely affected their growth. Short-time exposure of plants to N2O5 gas mitigated its toxicity and was able to support growth. Moreover, when the exposure of N2O5 and the contact with plants were physically separated, plants cultured under nitrogen deficiency were able to grow. This study shows that N2O5 gas generated from atmospheric nitrogen can be used as an effective nutrient for plants, indicating its potential to serve as an alternative nitrogen fertilization method for promoting plant growth.

The Reactivity of Ptn + Clusters With N2O Facilitated by Dual Lewis-Acid Sites.

The size dependence of metal cluster reactions frequently reveals valuable information on the mechanism of nanometal catalysis. Here, the reactivity of the Ptn + (n = 1-40) clusters with N2O is studied and a significant dependence on the size of these clusters is noticed. Interestingly, the small Ptn + clusters like Pt3 + and Pt4 + are inclined to form N2O complexes; some larger clusters, such as Pt19 +, Pt21 +, and Pt23 +, appear to be unreactive; however, the others such as Pt3 , 9,15 + and Pt18 + are capable of decomposing N2O. While Pt9 + rapidly reacts with N2O to form a stable quasitetrahedron Pt9O+ product, Pt18 + experiences a series of N2O decompositions to produce Pt18O1-7 +. Utilizing high-precision theoretical calculations, it is shown how the atomic structures and active sites of Ptn + clusters play a vital role in determining their reactivity. Cooperative dual Lewis-acid sites (CDLAS) can be achieved on specific metal clusters like Pt18 +, rendering accelerated N2O decomposition via both N- and O-bonding on the neighboring Pt atoms. The influence of CDLAS on the size-dependent reaction of Pt clusters with N2O is illustrated, offering insights into cluster catalysis in reactions that include the donation of electron pairs.

Revisiting the metal sites of nitrous oxide reductase in a low-dose structure from Marinobacter nauticus.

Copper-containing nitrous oxide reductase catalyzes a 2-electron reduction of the green-house gas N2O to yield N2. It contains two metal centers, the binuclear electron transfer site CuA, and the unique, tetranuclear CuZ center that is the site of substrate binding. Different forms of the enzyme were described previously, representing variations in oxidation state and composition of the metal sites. Hypothesizing that many reported discrepancies in the structural data may be due to radiation damage during data collection, we determined the structure of anoxically isolated Marinobacter nauticus N2OR from diffraction data obtained with low-intensity X-rays from an in-house rotating anode generator and an image plate detector. The data set was of exceptional quality and yielded a structure at 1.5 Å resolution in a new crystal form. The CuA site of the enzyme shows two distinct conformations with potential relevance for intramolecular electron transfer, and the CuZ cluster is present in a [4Cu:2S] configuration. In addition, the structure contains three additional types of ions, and an analysis of anomalous scattering contributions confirms them to be Ca2+, K+, and Cl-. The uniformity of the present structure supports the hypothesis that many earlier analyses showed inhomogeneities due to radiation effects. Adding to the earlier description of the same enzyme with a [4Cu:S] CuZ site, a mechanistic model is presented, with a structurally flexible CuZ center that does not require the complete dissociation of a sulfide prior to N2O binding.

Global nitrous oxide emissions from livestock manure during 1890-2020: An IPCC tier 2 inventory.

Nitrous oxide (N2O) emissions from livestock manure contribute significantly to the growth of atmospheric N2O, a powerful greenhouse gas and dominant ozone-depleting substance. Here, we estimate global N2O emissions from livestock manure during 1890-2020 using the tier 2 approach of the 2019 Refinement to the 2006 IPCC Guidelines. Global N2O emissions from livestock manure increased by ~350% from 451 [368-556] Gg N year-1 in 1890 to 2042 [1677-2514] Gg N year-1 in 2020. These emissions contributed ~30% to the global anthropogenic N2O emissions in the decade 2010-2019. Cattle contributed the most (60%) to the increase, followed by poultry (19%), pigs (15%), and sheep and goats (6%). Regionally, South Asia, Africa, and Latin America dominated the growth in global emissions since the 1990s. Nationally, the largest emissions were found in India (329 Gg N year-1), followed by China (267 Gg N year-1), the United States (163 Gg N year-1), Brazil (129 Gg N year-1) and Pakistan (102 Gg N year-1) in the 2010s. We found a substantial impact of livestock productivity, specifically animal body weight and milk yield, on the emission trends. Furthermore, a large spread existed among different methodologies in estimates of global N2O emission from livestock manure, with our results 20%-25% lower than those based on the 2006 IPCC Guidelines. This study highlights the need for robust time-variant model parameterization and continuous improvement of emissions factors to enhance the precision of emission inventories. Additionally, urgent mitigation is required, as all available inventories indicate a rapid increase in global N2O emissions from livestock manure in recent decades.

Sources of nitrous oxide emissions from agriculturally managed peatlands.

The draining and fertilization of peatlands for agriculture is globally an important source of the greenhouse gas nitrous oxide (N2 O). Hitherto, the contribution of major sources to the N2 O emission-that is, fertilization and nitrogen (N) release from peat decomposition-has not yet been deciphered. This hampers the development of smart mitigation strategies, considering that rewetting to halt peat decomposition and reducing N fertilization are promising N2 O emission-reduction strategies. Here, we used machine learning techniques and global N2 O observational data to generalize the distribution of N2 O emissions from agriculturally managed peatlands, to distinguish the sources of N2 O emissions, and to compare mitigation options. N2 O emissions from agriculturally managed croplands were 401.0 (344.5-470.9) kt N year-1 , with 121.6 (88.6-163.3) kt N year-1 contributed by fertilizer N. On grasslands, 64.0 (54.6-74.7) kt N2 O-N year-1 were emitted, with 4.6 (3.7-5.7) kt N2 O-N year-1 stemming from fertilizer N. The fertilizer-induced N2 O emission factor ranged from 1.5% to 3.2%. Reducing the current fertilizer input by 20% could achieve a 10% N2 O emission reduction for croplands but only 3% for grasslands. Rewetting 1.9 Mha cropland and 0.26 Mha grassland would achieve the same N2 O emission reductions. Our results suggest that N2 O mitigation strategies for managed peatlands should be considered separately across land-use types and climatic zones. For croplands, particularly in the tropics, relevant N2 O mitigation potentials are achievable through both fertilizer N reduction and peatland rewetting. For grasslands, management schemes to halt peat degradation (e.g. rewetting) should be considered preferentially for mitigating N2 O and contributing to meeting climate goals.

Effects of whole-soil warming on CH4 and N2 O fluxes in an alpine grassland.

Global climate warming could affect the methane (CH4 ) and nitrous oxide (N2 O) fluxes between soils and the atmosphere, but how CH4 and N2 O fluxes respond to whole-soil warming is unclear. Here, we for the first time investigated the effects of whole-soil warming on CH4 and N2 O fluxes in an alpine grassland ecosystem on the Tibetan Plateau, and also studied the effects of experimental warming on CH4 and N2 O fluxes across terrestrial ecosystems through a global-scale meta-analysis. The whole-soil warming (0-100 cm, +4°C) significantly elevated soil N2 O emission by 101%, but had a minor effect on soil CH4 uptake. However, the meta-analysis revealed that experimental warming did not significantly alter CH4 and N2 O fluxes, and it may be that most field warming experiments could only heat the surface soils. Moreover, the warming-induced higher plant litter and available N in soils may be the main reason for the higher N2 O emission under whole-soil warming in the alpine grassland. We need to pay more attention to the long-term response of greenhouse gases (including CH4 and N2 O fluxes) from different soil depths to whole-soil warming over year-round, which could help us more accurately assess and predict the ecosystem-climate feedback under realistic warming scenarios in the future.

Enhanced nitrous oxide emission factors due to climate change increase the mitigation challenge in the agricultural sector.

Effective nitrogen fertilizer management is crucial for reducing nitrous oxide (N2O) emissions while ensuring food security within planetary boundaries. However, climate change might also interact with management practices to alter N2O emission and emission factors (EFs), adding further uncertainties to estimating mitigation potentials. Here, we developed a new hybrid modeling framework that integrates a machine learning model with an ensemble of eight process-based models to project EFs under different climate and nitrogen policy scenarios. Our findings reveal that EFs are dynamically modulated by environmental changes, including climate, soil properties, and nitrogen management practices. Under low-ambition nitrogen regulation policies, EF would increase from 1.18%-1.22% in 2010 to 1.27%-1.34% by 2050, representing a relative increase of 4.4%-11.4% and exceeding the IPCC tier-1 EF of 1%. This trend is particularly pronounced in tropical and subtropical regions with high nitrogen inputs, where EFs could increase by 0.14%-0.35% (relative increase of 11.9%-17%). In contrast, high-ambition policies have the potential to mitigate the increases in EF caused by climate change, possibly leading to slight decreases in EFs. Furthermore, our results demonstrate that global EFs are expected to continue rising due to warming and regional drying-wetting cycles, even in the absence of changes in nitrogen management practices. This asymmetrical influence of nitrogen fertilizers on EFs, driven by climate change, underscores the urgent need for immediate N2O emission reductions and further assessments of mitigation potentials. This hybrid modeling framework offers a computationally efficient approach to projecting future N2O emissions across various climate, soil, and nitrogen management scenarios, facilitating socio-economic assessments and policy-making efforts.

Soil N2 O emissions from specialty crop systems: A global estimation and meta-analysis.

Nitrous oxide (N2 O) exacerbates the greenhouse effect and thus global warming. Agricultural management practices, especially the use of nitrogen (N) fertilizers and irrigation, increase soil N2 O emissions. As a vital sector of global agriculture, specialty crop systems usually require intensive input and management. However, soil N2 O emissions from global specialty crop systems have not been comprehensively evaluated. Here, we synthesized 1137 observations from 114 published studies, conducted a meta-analysis to evaluate the effects of agricultural management and environmental factors on soil N2 O emissions, and estimated global soil N2 O emissions from specialty crop systems. The estimated global N2 O emission from specialty crop soils was 1.5 Tg N2 O-N year-1 , ranging from 0.5 to 4.5 Tg N2 O-N year-1 . Globally, soil N2 O emissions exponentially increased with N fertilizer rates. The effect size of N fertilizer on soil N2 O emissions generally increased with mean annual temperature, mean annual precipitation, and soil organic carbon concentration but decreased with soil pH. Global climate change will further intensify the effect of N fertilizer on soil N2 O emissions. Drip irrigation, fertigation, and reduced tillage can be used as essential strategies to reduce soil N2 O emissions and increase crop yields. Deficit irrigation and non-legume cover crop can reduce soil N2 O emissions but may also lower crop yields. Biochar may have a relatively limited effect on reducing soil N2 O emissions but be effective in increasing crop yields. Our study points toward effective management strategies that have substantial potential for reducing N2 O emissions from global agricultural soils.

Climate mitigation potential of cover crops in the United States is regionally concentrated and lower than previous estimates.

Widespread adoption of regenerative agriculture practices is an integral part of the US plan to achieve net-zero greenhouse gas emissions by 2050. National incentives have particularly increased for the adoption of cover crops (CCs), which have presumably large carbon (C) sequestration potential. However, assessments of national CC climate benefits have not fully considered regional variability, changing C sequestration rates over time, and potential N2O trade-offs. Using the DayCent soil biogeochemical model and current national survey data, we estimate CC climate change mitigation potential to be 39.0 ± 24.1 Mt CO2e year-1, which is 45%-65% lower than previous estimates, with large uncertainty attributed to N2O impacts. Three-fourths of this climate change mitigation potential is concentrated in the North Central, Southern Great Plains and Lower Mississippi regions. Public investment should be focused in these regions to maximize CC climate benefits, but the national contribution of CC to emissions targets may be lower than previously anticipated.

The Oscillatory Behaviour of Cu-ZSM-5 Catalysts for N2O Decomposition: Investigation of Cu Species by Complementary Techniques.

Copper-exchanged ZSM-5 (Cu-ZSM-5) is a promising catalyst thanks to the Cu redox pair. A particular feature of this material consists in the presence of spontaneous isothermal oscillations which take place during N2O decomposition reaction, depending on the operating conditions. In the present work, a set of five Cu-ZSM-5 catalysts was synthesised by three procedures and three different copper precursor concentrations: i) wet impregnation, ii) single ion exchange, and iii) double ion exchange. Catalytic tests revealed that the ion-exchanged samples exhibit a low catalytic activity and no oscillatory behaviour, except for the twice-exchanged sample which achieves an average N2O conversion of 26 % at 400 °C. Conversely, the impregnated samples reach higher levels of N2O conversion (66 % for Cu5ZSM5_WI and 72 % for Cu10ZSM5_WI) and demonstrate a similar oscillating pattern. Further investigations disclosed that the most active catalysts, characterised by the presence of oscillatory behaviour, have more abundant and easily reducible copper species (ICP, EDX and H2-TPR) which interact better with the zeolitic support (FT-IR). Catalytic tests under a long time on stream (TOS) suggest that either self-organised patterns or deterministic chaos can be achieved during the reaction, depending on the operating conditions, such as temperature and contact time.

Diversity and Activity of Soil N2O-Reducing Bacteria Shaped by Urbanization.

Nitrous oxide (N2O) is a potent greenhouse gas with various production pathways. N2O reductase (N2OR) is the primary N2O sink, but the distribution of its gene clades, typically nosZI and atypically nosZII, along urbanization gradients remains poorly understood. Here we sampled soils from forests, parks, and farmland across eight provinces in eastern China, using high-throughput sequencing to distinguish between two N2O-reducing bacteria clades. A deterministic process mainly determined assemblies of the nosZI communities. Homogeneous selection drove nosZI deterministic processes, and both homogeneous and heterogeneous selection influenced nosZII. This suggests nosZII is more sensitive to environmental changes than nosZI, with significant changes in community structure over time or space. Ecosystems with stronger anthropogenic disturbance, such as urban areas, provide diverse ecological niches for N2O-reducing bacteria (especially nosZII) to adapt to environmental fluctuations. Structural equation modeling (SEM) and correlation analyses revealed that pH significantly influences the community composition of both N2O-reducing bacteria clades. This study underscores urbanization's impact on N2O-reducing bacteria in urban soils, highlighting the importance of nosZII and survival strategies. It offers novel insights into the role of atypical denitrifiers among N2O-reducing bacteria, underscoring their potential ecological importance in mitigating N2O emissions from urban soils.

Hydrologic Connectivity Regulates Riverine N2O Sources and Dynamics.

Indirect nitrous oxide (N2O) emissions from streams and rivers are a poorly constrained term in the global N2O budget. Current models of riverine N2O emissions place a strong focus on denitrification in groundwater and riverine environments as a dominant source of riverine N2O, but do not explicitly consider direct N2O input from terrestrial ecosystems. Here, we combine N2O isotope measurements and spatial stream network modeling to show that terrestrial-aquatic interactions, driven by changing hydrologic connectivity, control the sources and dynamics of riverine N2O in a mesoscale river network within the U.S. Corn Belt. We find that N2O produced from nitrification constituted a substantial fraction (i.e., >30%) of riverine N2O across the entire river network. The delivery of soil-produced N2O to streams was identified as a key mechanism for the high nitrification contribution and potentially accounted for more than 40% of the total riverine emission. This revealed large terrestrial N2O input implies an important climate-N2O feedback mechanism that may enhance riverine N2O emissions under a wetter and warmer climate. Inadequate representation of hydrologic connectivity in observations and modeling of riverine N2O emissions may result in significant underestimations.

Tandem Catalysis for Simultaneous Removal of NOx and C3H8 with Inhibition of N2O.

Tandem catalysis is widely adopted for multipollutant control in mobile sources but has rarely been reported in stationary source emission elimination. This work proposed a tandem arrangement way with up-streamed V2O5/TiO2 + down-streamed Cr2O3/TiO2 catalysts, which could achieve the efficient synergistic control of NOx and C3H8 in industrial flue gas. Moreover, this arrangement successfully alleviated the unwanted N2O formation during the NH3 -SCR process. Compared to the conventional impregnation method of the Cr2O3-V2O5/TiO2 catalyst, the tandem catalysts of V2O5/TiO2 + Cr2O3/TiO2 could enhance the NOx and C3H8 conversion by 4.2% and 39.5%, respectively, at 350 °C. It might be attributed to the fact that Cr species was the active site for C3H8 oxidation, and the tandem arrangement of catalysts was beneficial to even dispersion of active components on supports. Furthermore, due to the preferential NOx removal over the up-streamed V2O5/TiO2 catalyst, the tandem catalysts obviously alleviated the N2O formation caused by Cr species during the NH3-SCR process. Herein, it significantly decreased N2O formation by 240.5% at 350 °C compared to the Cr2O3-V2O5/TiO2 catalyst, achieving multipollutant emission control from industrial flue gas with the performance of "one stone three birds".

Boosting N2O Decomposition by Fabricating the Cs-O-Co Structure over Co3O4 with Single-Layer Atoms of Cs.

Developing effective catalysts for N2O decomposition at low temperatures is challenging. Herein, the Cs-O-Co structure, as the active species fabricated by single-layer atoms of Cs over pure Co3O4, originally exhibited great catalytic activity of N2O decomposition in simulated vehicle exhaust and flue gas from nitric acid plants. A similar catalytic performance was also observed for Na, K, and Rb alkali metals over Co3O4 catalysts for N2O decomposition, illustrating the prevalence of alkali-metal-promotion over Co3O4 in practical applications. The catalytic results indicated that the TOF of Co3O4 catalysts loaded by 4 wt% Cs was nearly 2 orders of magnitude higher than that of pure Co3O4 catalysts at 300 °C. Interestingly, the conversions of N2O decomposition over Co3O4 catalysts doped by the same Cs loadings were significantly inhibited. Characterization results indicated that the primary active Cs-O-Co structure was formed by highly orbital hybridization between the Cs 6s and the O 2p orbital over the supported Co3O4 catalysts, where Cs could donate electrons to Co3+ and produce much more Co2+. In contrast, the doped Co3O4 catalysts were dominated by Cs2O2 species; meanwhile, CsOH species was generated by adsorbed water vapor led to a significant decrease in catalytic activity. In situ DRIFTS, rigorous kinetics, and DFT results elaborated the reaction mechanism of N2O decomposition, where the direct decomposition of adsorbed N2O was the kinetically relevant step over supported catalysts in the absence of O2. Meanwhile, the assistance of adsorbed N2O decomposition by activated oxygen was observed as the kinetically relevant step in the presence of O2. The results may pave a promising path toward developing alkali-metal-promotion catalysts for efficient N2O decomposition.

Influence of Oxygen Vacancy-Induced Coordination Change on Pd/CeO2 for NO Reduction.

The byproduct formation in environmental catalysis is strongly influenced by the chemical state and coordination of catalysts. Herein, two Pd/CeO2 catalysts (PdCe-350 and PdCe-800) with varying oxygen vacancies (Ov) and coordination numbers (CN) of Pd were prepared to investigate the mechanism of N2O and NH3 formation during NO reduction by CO. PdCe-350 exhibits a higher density of Ov and Pd sites with higher CN, leading to an enhanced metal-support interaction by electron transformation from the support to Pd. Consequently, PdCe-350 displayed increased levels of byproduct formation. In situ spectroscopies under dry and wet conditions revealed that at low temperatures, the N2O formation strongly correlated with the Ov density through the decomposition of chelating nitro species on PdCe-350. Conversely, at high temperatures, it was linked to the reactivity of Pd species, primarily facilitated by monodentate nitrates on PdCe-800. In terms of NH3 formation, its occurrence was closely associated with the activation of H2O and C3H6, since a water-gas shift or hydrocarbon reforming could provide hydrogen. Both bridging and monodentate nitrates showed activity in NH3 formation, while hyponitrites were identified as key intermediates for both catalysts. The insights provide a fundamental understanding of the intricate relationship among the local coordination of Pd, surface Ov, and byproduct distribution.

Boosting N2O Catalytic Decomposition by the Synergistic Effect of Multiple Elements in Cobalt-Based High-Entropy Oxides.

Nitrous oxide (N2O) has a detrimental impact on the greenhouse effect, and its efficient catalytic decomposition at low temperatures remains challenging. Herein, the cobalt-based high-entropy oxide with a spinel-type structure (Co-HEO) is successfully fabricated via a facile coprecipitation method for N2O catalytic decomposition. The obtained Co-HEO catalyst displays more remarkable catalytic performance and higher thermal stability compared with single and binary Co-based oxides, as the temperature of 90% N2O decomposition (T90) is 356 °C. A series of characterization results reveal that the synergistic effect of multiple elements enhances the reducibility and augments oxygen vacancy in the high-entropy system, thus boosting the activity of the Co-HEO catalyst. Moreover, density functional theory (DFT) calculations and the temperature-programmed surface reaction (TPSR) with isotope labeling demonstrate that N2O decomposition on the Co-HEO catalyst follows the Langmuir-Hinshelwood (L-H) mechanism with the promotion of abundant oxygen vacancies. This work provides a fundamental understanding of the synergistic catalytic effect in N2O decomposition and paves the way for the novel environmental catalytic applications of HEO.