Paddy rice methane emissions, controlling factors, and mitigation potentials across Monsoon Asia.

Rice is a staple food for more than half of humanity, and 90 % of rice is grown and consumed in Asia. However, paddy rice cultivation creates an ideal environment for the production and release of methane (CH4). How to estimate regional CH4 emissions accurately and how to mitigate them efficiently have been of key concern. Here, with a machine learning method, we investigate the spatiotemporal changes, the major controlling factors and mitigation potentials of paddy rice CH4 emissions across Monsoon Asia at a resolution of 0.1° (∼10 km). Spatially CH4 emissions are highly heterogeneous, with the Indo-Gangetic Plain, Deltas of the Mekong, and Yangtze River Basin as the hotspots. Nationwide, China, India, Bangladesh and Vietnam are the major emitters. Straw applied on season is a critical controlling factor for CH4 emission in rice fields. The single-season rice contributes to over 80 % of the total emissions. CH4 emissions from Monsoon Asia have notably declined since 2007. Three mitigation strategies, including water management techniques, off-season straw return, and straw to biochar, may reduce CH4 emissions by 27.66 %, 23.78 %, and 21.79 %, respectively, with the most effective strategy being rice cultivation type-specific and environment-specific. Our findings gain new insights into CH4 emissions and mitigations across Monsoon Asia, providing evidence to adopt precise mitigation strategies based on rice cultivation types and local environment.

Ferro/Nonferroelectric Vertical Heterostructure Superlattice as a Visible-Light-Responsive Photocatalyst: A DFT Prediction.

Developing narrow-band-gap ferroelectric semiconducting photocatalysts is a promising strategy for efficient photocatalytic water splitting with high energy conversion efficiency. Within this context, six ferro/nonferroelectric vertical heterostructure superlattices (VHSs) are constructed in this work by stacking ferroelectric SiS or GeS with nonferroelectric layered organic photocatalysts (C2N, g-C3N4, and melon), layer by layer. The geometry and electronic structures of these six VHSs are systematically investigated by density functional theory calculations. Consequently, four VHSs (SiS/g-C3N4, GeS/C2N, GeS/g-C3N4, and GeS/melon) are predicted to simultaneously possess several important and highly desirable features for photocatalytic water splitting, namely excellent visible-light adsorption, remarkable spontaneous polarization (0.49-0.70 C/m2), spatial charge separation, as well as suitable band-edge positions, thus serving as potential candidates for photocatalytic water splitting to produce hydrogen. This work not only provides a new strategy to use narrow-band-gap ferroelectric semiconductors for photocatalytic water splitting but also offers inspiration for developing photocatalysts with high energy conversion efficiency.

Gradient tungsten-doped Bi3TiNbO9 ferroelectric photocatalysts with additional built-in electric field for efficient overall water splitting.

Bi3TiNbO9, a layered ferroelectric photocatalyst, exhibits great potential for overall water splitting through efficient intralayer separation of photogenerated carriers motivated by a depolarization field along the in-plane a-axis. However, the poor interlayer transport of carriers along the out-of-plane c-axis, caused by the significant potential barrier between layers, leads to a high probability of carrier recombination and consequently results in low photocatalytic activity. Here, we have developed an efficient photocatalyst consisting of Bi3TiNbO9 nanosheets with a gradient tungsten (W) doping along the c-axis. This results in the generation of an additional electric field along the c-axis and simultaneously enhances the magnitude of depolarization field within the layers along the a-axis due to strengthened structural distortion. The combination of the built-in field along the c-axis and polarization along the a-axis can effectively facilitate the anisotropic migration of photogenerated electrons and holes to the basal {001} surface and lateral {110} surface of the nanosheets, respectively, enabling desirable spatial separation of carriers. Hence, the W-doped Bi3TiNbO9 ferroelectric photocatalyst with Rh/Cr2O3 cocatalyst achieves an efficient and durable overall water splitting feature, thereby providing an effective pathway for designing excellent layered ferroelectric photocatalysts.

Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Amplification of oxidative stress by lipid surface-coated single-atom Au nanozymes for oral cancer photodynamic therapy.

Single-atom nanozymes (SANs) are the latest trend in biomaterials research and promote the application of single atoms in biological fields and the realization of protein catalysis in vivo with inorganic nanoparticles. Carbon quantum dots (CDs) have excellent biocompatibility and fluorescence properties as a substrate carrying a single atom. It is difficult to break through pure-phase single-atom materials with quantum dots as carriers. In addition, there is currently no related research in the single-atom field in the context of oral cancer, especially head and neck squamous cell carcinoma. This research developed a lipid surface-coated nanozyme combined with CDs, single-atomic gold, and modified lipid ligands (DSPE-PEG) with transferrin (Tf) to treat oral squamous cell carcinoma. The study results have demonstrated that surface-modified single-atom carbon quantum dots (m-SACDs) exhibit excellent therapeutic effects and enable in situ image tracking for diagnosing and treating head and neck squamous carcinoma (HNSCC).

Quantifying the policy-driven large scale vegetation restoration effects on evapotranspiration over drylands in China.

Evapotranspiration (ET) is a key variable in the water cycle and reflects the ecosystem's feedback into the climate system. However, quantitative studies on the response of ET to large-scale vegetation restoration projects and climate change are still lacking, especially in drylands. To address this deficiency, this research examined the variation in ET since the implementation of restoration projects in the drylands of China in 2000-2018, and utilized quantitative analysis methods to investigate the effects of six environmental factors, including temperature (TEM), precipitation (PRE), solar radiation (RAD), vapour pressure deficit (VPD), soil moisture (SM), and leaf area index (LAI) on ET. Furthermore, a new method was proposed to detect the ET change caused by land use and land cover change (LUCC). The results indicated that ET showed a significant increasing trend (3.54 mm yr-1) during 2000-2018, and PRE was identified as a main influential factor with an ET contribution rate of more than 50%, especially in areas with insignificant vegetation greening. Additionally, the LAI had a major positive impact on ET in the areas of significant vegetation greening, and the contribution rate was nearly 40%. Furthermore, large-scale vegetation restoration expanded the area of high-transpiration vegetation types, and the ΔET (net variable quantity of ET caused by LUCC) increased obviously especially for the changes from cropland and grassland to forest, and barren land to grassland. These findings provide a new perspective for future assessments and further decision making regarding vegetation restoration projects in drylands.

Facilitating two-electron oxygen reduction with pyrrolic nitrogen sites for electrochemical hydrogen peroxide production.

Electrocatalytic hydrogen peroxide (H2O2) production via the two-electron oxygen reduction reaction is a promising alternative to the energy-intensive and high-pollution anthraquinone oxidation process. However, developing advanced electrocatalysts with high H2O2 yield, selectivity, and durability is still challenging, because of the limited quantity and easy passivation of active sites on typical metal-containing catalysts, especially for the state-of-the-art single-atom ones. To address this, we report a graphene/mesoporous carbon composite for high-rate and high-efficiency 2e- oxygen reduction catalysis. The coordination of pyrrolic-N sites -modulates the adsorption configuration of the *OOH species to provide a kinetically favorable pathway for H2O2 production. Consequently, the H2O2 yield approaches 30 mol g-1 h-1 with a Faradaic efficiency of 80% and excellent durability, yielding a high H2O2 concentration of 7.2 g L-1. This strategy of manipulating the adsorption configuration of reactants with multiple non-metal active sites provides a strategy to design efficient and durable metal-free electrocatalyst for 2e- oxygen reduction.

Selective Exposure of Robust Perovskite Layer of Aurivillius-Type Compounds for Stable Photocatalytic Overall Water Splitting.

Aurivillius-type compounds ((Bi2 O2 )2+ (An -1 Bn O3 n +1 )2- ) with alternately stacked layers of bismuth oxide (Bi2 O2 )2+ and perovskite (An -1 Bn O3 n +1 )2- are promising photocatalysts for overall water splitting due to their suitable band structures and adjustable layered characteristics. However, the self-reduction of Bi3+ at the top (Bi2 O2 )2+ layers induced by photogenerated electrons during photocatalytic processes causes inactivation of the compounds as photocatalysts. Here, using Bi3 TiNbO9 as a model photocatalyst, its surface termination is modulated by acid etching, which well suppresses the self-corrosion phenomenon. A combination of comprehensive experimental investigations together with theoretical calculations reveals the transition of the material surface from the self-reduction-sensitive (Bi2 O2 )2+ layer to the robust (BiTiNbO7 )2- perovskite layer, enabling effective electron transfer through surface trapping and effective hole transfer through surface electric field, and also efficient transfer of the electrons to the cocatalyst for greatly enhanced photocatalytic overall water splitting. Moreover, this facile modification strategy can be readily extended to other Aurivillius compounds (e.g., SrBi2 Nb2 O9 , Bi4 Ti3 O12 , and SrBi4 Ti4 O15 ) and therefore justify its usefulness in rationally tailoring surface structures of layered photocatalysts for high photocatalytic overall water-splitting activity and stability.

One-Dimensional π-d Conjugated Conductive Metal-Organic Framework with Dual Redox-Active Sites for High-Capacity and Durable Cathodes for Aqueous Zinc Batteries.

Aqueous Zn-based batteries (ZIBs) possess huge advantages in terms of high safety, low cost, and environmental friendliness. However, the lack of suitable cathodes with high-capacity, long-cycling, and high-rate capability limits their practical application. Herein, we present a highly crystalline one-dimensional π-d conjugated conductive metal-organic framework by coordinating ultrasmall 1,2,4,5-benzenetetramine (BTA) linkers with copper ions (Cu-BTA-H), as a cathode for ZIBs. The large ratio of active sites and dual redox mechanism of Cu-BTA-H, including the one-electron-redox reaction over copper ions (via Cu2+/Cu+) and the two-electron-redox reaction over organic ligands (via C═N/C-N), effectively enhance its reversible capacity. Meanwhile, the abundant porosity, small band gap, high crystallinity, and stable coordination structure of Cu-BTA-H endow it with fast ion/electron transport and effectively hinder the dissolution of organic ligands during cycling, respectively. Consequently, Cu-BTA-H possesses a high reversible capacity of 330 mAh g-1 at 200 mA g-1 and excellent rate performance and long-cycle stability, with a high capacity of 106.1 mAh g-1 at 2.0 A g-1 after 500 cycles and a high Coulombic efficiency of ∼100%. The proposed conductive MOFs with dual redox-active sites provide an efficient approach for constructing fast, stable, and high-capacity energy storage devices.

Composite non-noble system with bridging oxygen for catalyzing Tafel-type alkaline hydrogen evolution.

Using hydrogen as a fuel is an effective way to combat energy crisis and at the same time reduce greenhouse gas emission. Alkaline hydrogen evolution reaction (HER) is one important way to obtain green hydrogen, which however is energy intensive and is difficult to obtain high efficiencies even when using state-of-the-art noble metal catalysts. Here, we report a three-component catalytic system using only non-noble elements, consisting of cobalt oxide clusters and single molybdenum atoms supported on oxyanion-terminated two-dimensional MXene, which enabled the unusual generation of hydrogen by a kinetically fast Volmer-Tafel process in an alkaline electrolyte. The key feature of this catalyst is that the three components are connected by bridging oxygen, which serves to immediately adsorb H* produced during water dissociation on cobalt oxide and relay it to the molybdenum single-atom catalyst. On the Mo atom, due to this unique coordination environment, the relayed H* intermediates directly combine and desorb, realizing H2 generation through an unusual Tafel pathway. The presence of bridging oxygen increases the acidity of the catalyst as Brønsted acid with the reversible adsorption and donation of a proton, thus eliminating the need for acid addition and ensuring excellent and sustainable alkaline HER performance. The performance of our catalyst is comparable to that of the commercial noble metal catalyst PtRu/C. Our work makes a significant contribution to designing efficient non-noble catalysts for alkaline HER electrocatalysis.

Manipulating Selectivity of Hydroxyl Radical Generation by Single-Atom Catalysts in Catalytic Ozonation: Surface or Solution.

Hydroxyl radical-dominated oxidation in catalytic ozonation is, in particular, important in water treatment scenarios for removing organic contaminants, but the mechanism about ozone-based radical oxidation processes is still unclear. Here, we prepared a series of transitional metal (Co, Mn, Ni) single-atom catalysts (SACs) anchored on graphitic carbon nitride to accelerate ozone decomposition and produce highly reactive ·OH for oxidative destruction of a water pollutant, oxalic acid (OA). We experimentally observed that, depending on the metal type, OA oxidation occurred dominantly either in the bulk phase, which was the case for the Mn catalyst, or via a combination of the bulk phase and surface reaction, which was the case for the Co catalyst. We further performed density functional theory simulations and in situ X-ray absorption spectroscopy to propose that the ozone activation pathway differs depending on the oxygen binding energy of metal, primarily due to differential adsorption of O3 onto metal sites and differential coordination configuration of a key intermediate species, *OO, which is collectively responsible for the observed differences in oxidation mechanisms and kinetics.

Photocatalytic Overall Water Splitting over PbTiO3 Modulated by Oxygen Vacancy and Ferroelectric Polarization.

Ferroelectric materials hold great promise in the field of photocatalytic water splitting due to their spontaneous polarization that sets up an inherent internal field for the spatial separation of photogenerated charges. The ferroelectric polarization, however, is generally accompanied by some intrinsic defects, particularly oxygen vacancies, whose impact upon photocatalysis is far from being fully understood and modulated. Here, we have studied the role of oxygen vacancies over the photocatalytic behavior of single-domain PbTiO3 through a combination of theoretical and experimental viewpoints. Our results indicate that the oxygen vacancies in the negatively polarized facet (001) are active sites for water oxidation into O2, while the defect-free sites prefer H2O2 as the oxidation product. The apparent quantum yield at 435 nm for photocatalytic overall water splitting with PbTiO3/Rh/Cr2O3 is determined to be 0.025%, which is remarkable for single undoped metal oxide-based photocatalysts. Furthermore, the strong correlation among oxygen vacancies, polarization strength, and photocatalytic activity is properly reflected by charge separation conditions in the single-domain PbTiO3. This work clarifies the crucial role of oxygen vacancies during photocatalytic reactions of PbTiO3, which provides a useful guide to the design of efficient ferroelectric photocatalysts and their water redox reaction pathways.

A polymer electrolyte design enables ultralow-work-function electrode for high-performance optoelectronics.

Ambient solution-processed conductive materials with a sufficient low work function are essential to facilitate electron injection in electronic and optoelectronic devices but are challenging. Here, we design an electrically conducting and ambient-stable polymer electrolyte with an ultralow work function down to 2.2 eV, which arises from heavy n-doping of dissolved salts to polymer matrix. Such materials can be solution processed into uniform and smooth films on various conductors including graphene, conductive metal oxides, conducting polymers and metals to substantially improve their electron injection, enabling high-performance blue light-emitting diodes and transparent light-emitting diodes. This work provides a universal strategy to design a wide range of stable charge injection materials with tunable work function. As an example, we also synthesize a high-work-function polymer electrolyte material for high-performance solar cells.

An Ultrahigh Rate and Stable Zinc Anode by Facet-Matching-Induced Dendrite Regulation.

Resource-abundant metal (e.g., zinc) batteries feature intrinsic advantages of safety and sustainability. Their practical feasibility, however, is impeded by the poor reversibility of metal anodes, typically caused by the uncontrollable dendrite enlargement. Significant effort is exerted to completely prevent dendrites from forming, but this seems less effective at high current densities. Herein, this work presents an alternative dendrite regulation strategy of forming tiny, homogeneously distributed, and identical zinc dendrites by facet matching, which effectively avoids undesirable dendrite enlargement. Confirmed by multiscale theoretical screening and characterization, the regularly exposed Cu(111) facets at the ridges of a copper nanowire are capable of such dendrite regulation by forming a low-mismatched Zn(002)/Cu(111) interface. Consequently, reversible zinc electroplating/stripping is achieved at an unprecedentedly high rate of 100 mA cm-2 for over 30 000 cycles, corresponding to an accumulative areal capacity up to 30 Ah cm-2 . A full cell using this anode shows a high capacity of 308.3 mAh g-1 and a high capacity retention of 91.4% after 800 cycles. This strategy is also viable for magnesium and aluminum anodes, thus opening up a promising and universal avenue toward long-life and high-rate metal anodes.

Steering surface reconstruction of copper with electrolyte additives for CO2 electroreduction.

Electrocatalytic CO2 reduction to value-added hydrocarbon products using metallic copper (Cu) catalysts is a potentially sustainable approach to facilitate carbon neutrality. However, Cu metal suffers from unavoidable and uncontrollable surface reconstruction during electrocatalysis, which can have either adverse or beneficial effects on its electrocatalytic performance. In a break from the current catalyst design path, we propose a strategy guiding the reconstruction process in a favorable direction to improve the performance. Typically, the controlled surface reconstruction is facilely realized using an electrolyte additive, ethylenediamine tetramethylenephosphonic acid, to substantially promote CO2 electroreduction to CH4 for commercial polycrystalline Cu. As a result, a stable CH4 Faradaic efficiency of 64% with a partial current density of 192 mA cm-2, thus enabling an impressive CO2-to-CH4 conversion rate of 0.25 µmol cm-2 s-1, is achieved in an alkaline flow cell. We believe our study will promote the exploration of electrochemical reconstruction and provide a promising route for the discovery of high-performance electrocatalysts.

Constructing Anatase-Brookite TiO2 Phase Junction by Thermal Topotactic Transition to Promote Charge Separation for Superior Photocatalytic H2 Generation.

Phase junctions of photocatalysts can promote the separation of photogenerated charge carriers for efficient utilization of the carriers. Construction of phase junctions and establishing their structure-performance relationship are still required. Herein, polycrystalline TiO2 decahedral plates with different phases were synthesized by thermal treatment-induced topotactic transition of titanium oxalate crystals. The phase of TiO2 evolved from pure anatase to anatase-brookite, anatase-brookite-rutile, and then to anatase-rutile, while the morphology of the decahedral plates was well maintained. The biphase anatase-brookite was found to be most efficient in photocatalytic hydrogen generation. Specifically, the hydrogen generation rate of the biphase anatase-brookite TiO2 was nearly 2.4 times greater than that of the biphase anatase-rutile TiO2. The spatially resolved surface photovoltage measurements indicate the more efficient separation of photogenerated charge carriers and thus greater photocatalytic activity of the former. This work provides a strategy for developing efficient phase-junction photocatalysts.

Surface Oxygen Vacancies Confined by Ferroelectric Polarization for Tunable CO Oxidation Kinetics.

Surface oxygen vacancies have been widely discussed to be crucial for tailoring the activity of various chemical reactions from CO, NO, to water oxidation by using oxide-supported catalysts. However, the real role and potential function of surface oxygen vacancies in the reaction remains unclear because of their very short lifetime. Here, it is reported that surface oxygen vacancies can be well confined electrostatically for a polarization screening near the perimeter interface between Pt {111} nanocrystals and the negative polar surface (001) of ferroelectric PbTiO3. Strikingly, such a catalyst demonstrates a tunable catalytic CO oxidation kinetics from 200 °C to near room temperature by increasing the O2 gas pressure, accompanied by the conversion curve from a hysteresis-free loop to one with hysteresis. The combination of reaction kinetics, electronic energy loss spectroscopy (EELS) analysis, and density functional theory (DFT) calculations, indicates that the oxygen vacancies stabilized by the negative polar surface are the active sites for O2 adsorption as a rate-determining step, and then dissociated O moves to the surface of the Pt nanocrystals for oxidizing adsorbed CO. The results open a new pathway for tunable catalytic activity of CO oxidation.

Spatiotemporal changes in greenhouse gas emissions and soil organic carbon sequestration for major cropping systems across China and their drivers over the past two decades.

Chinese agricultural systems have experienced dramatic changes in crop planting area, cropping system, irrigation and fertilization managements, and crop yields in recent decades. These changes can substantially affect greenhouse gases (GHG) emissions and soil organic carbon (SOC) sequestration in croplands. However, the spatiotemporal patterns, as well as their driving factors and mechanisms, have not been well understood. Here, the Denitrification-Decomposition model is calibrated and validated to estimate nitrous oxide (N2O) and methane (CH4) emissions and SOC sequestration for seven major cropping systems in China during 2001-2020. The Logarithmic Mean Divisia Index method is further applied to attribute the net GHG emissions (NGEs) trend to various drivers. The results show that the total N2O emissions, CH4 emissions, and SOC sequestration were approximately 23.7, 182.0, and 177.6 Tg CO2-eq/year in the croplands across China. The national average NGEs per unit area ranged from -8705 to 8431 kg CO2-eq ha-1 year-1 across the major cropping systems. During 2001-2020, the trend in national annual NGEs was 0.66 kg CO2-eq ha-1 year-2, ranging from -78.9 to 82.2 kg CO2-eq ha-1 year-2 across the major cropping systems. The paddy lands were mainly a carbon source due to the large amount of CH4 emissions while the uplands could be a carbon sink owing to SOC sequestration. As a whole, the cropland in China was a carbon source with the NGEs equal to 28.4 Tg CO2-eq/year, and the NGEs increased by 0.047 Tg CO2-eq/year2 in the past 20 years. Nationally, changes in crop planting area and yields reduced the NGEs whereas changes in nitrogen use efficiency and cropping systems increased them, although the major factors and their impacts varied greatly among regions. Optimizing cropping systems and nitrogen fertilization based on the local genotype, environment and management should be the most effective method to reduce the NGEs in croplands.

Interactive impacts of climate change and agricultural management on soil organic carbon sequestration potential of cropland in China over the coming decades.

Cropland plays an important role in Soil Organic Carbon (SOC) sequestration. Although the SOC stock and its dynamic in the past decades have been extensively investigated, the information as to where, how much, and how SOC could be potentially sequestered in the coming decades has rarely been available. Here, the Rothamsted Carbon model was applied to investigate the spatiotemporal pattern of SOC sequestration potential for China's cropland in 2021-2040 at 1 km resolution, as well as the interactive impacts of climate change and agricultural management on SOC sequestration. Under the combined impacts of climate change and C input, the SOC sequestration of China's cropland in 2021-2040 would be about 0.56 Mg C ha-1 (0.06% yr-1), 1.33 Mg C ha-1 (0.15% yr-1), 2.10 Mg C ha-1 (0.24% yr-1), and 3.65 Mg C ha-1 (0.41% yr-1), with no increase, 5%, 10%, and 20% increase of C input, respectively. Therefore, a >20% increase in C input would be necessary to realize the promise of the '4 per 1000' initiative. Climate change would decrease SOC sequestration by 26.6-27.6 Tg yr-1 (or 60.4-62.7%). An increase of C input by 0%, 5%, 10%, and 20% relative to business as usual (BAU) would increase SOC sequestration by 4.8 (or 10.8%), 6.6 (or 14.9%), 13.1 (or 29.8%), and 26.2 (or 59.6%) Tg yr-1, respectively. The contributions of temperature, precipitation, and C input to SOC sequestration will be averagely 18.6%, 22.4%, and 59.0%, respectively. Our findings quantify the SOC sequestration in 2021-2040 at a high spatial resolution under the interactive impacts of climate change and agricultural management, which help to identify potential foci and develop region-specific measures to increase SOC sequestration efficiently.