The urgency to mitigate environmental impacts from anthropogenic CO2 emissions has propelled extensive research efforts on CO2 reduction. The current work reports a novel approach involving transforming CO2 and ethane into carbon nanotubes (CNTs) using earth-abundant metals (Fe, Co, Ni) at 750 °C. This route facilitates long-term carbon storage via generating high-value CNTs and produces valuable syngas with adjustable H2/CO ratios as byproducts. Without CO2, direct pyrolysis of ethane undergoes rapid deactivation. The participation of CO2 not only enhances the durability of the catalyst, but also contributes about 30% of the CNTs production, presenting a viable solution to CO2 challenges. The CNT morphology depends on the catalyst used. Co- and Ni-based catalysts produce CNT with a 20 nm diameter and micrometer length, whereas Fe-based catalysts yield bamboo-like structures. This work represents a pioneering effort in utilizing CO2 and ethane for CNT production with potential environmental and economic benefits.
Acidic H2O2 synthesis through electrocatalytic 2e- oxygen reduction presents a sustainable alternative to the energy-intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e- oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial-level currents, resulting in an effective current densities of 50â421 mA cmâ2 with 84â100% Faradaic efficiency and a production rate of 856â7842 µmol cm-2 h-1 that far exceeds the performance observed in pure acidic electrolytes or low-current electrolysis. Finite-element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e- oxygen reduction through interacting with coordinated H2O.
Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.
Earth abundant transition metal nitrides (TMNs) are a promising group of catalysts for a wide range of thermocatalytic, electrocatalytic and photocatalytic reactions, with potential to achieve high activity and selectivity while reducing reliance on the use of Pt-group metals. However, current fundamental understanding of the active sites of these materials and the mechanisms by which selective transformations occur is somewhat lacking. Recent investigations of these materials from our group and others have utilized probe molecules, model surfaces, and in situ techniques to elucidate the origin of their activity, strong metal-support interactions, and unique d-band electronic structures. This Perspective discusses three classes of reactions for which TMNs have been used as case studies to highlight how these properties, along with synergistic interactions with metal overlayers, can be exploited to design active, selective and stable TMN catalysts. First, studies of the reactions of C1 molecules will be discussed, specifically highlighting the ability of TMNs to activate CO2. Second, the upgrading of biomass and biomass-derived oxygenates over TMN catalysts will be reviewed. Third, the use of TMNs for H2 production via water electrolysis will be discussed. Finally, we will discuss the challenges and future directions in the study of TMN catalysts, in particular expanding on opportunities to enhance fundamental mechanistic understanding using model surfaces, the elucidation of active centers via in situ techniques, and the development of efficient synthesis methods and design principles.
BACKGROUND: pOsNAR2.1:OsNAR2.1 expression could significantly increase nitrogen uptake efficiency and grain yield of rice. RESULT: This study reported the effects of overexpression of OsNAR2.1 by OsNAR2.1 promoter on physiological and agronomic traits associated with drought tolerance. In comparison to the wild-type (WT), the pOsNAR2.1:OsNAR2.1 transgenic lines exhibited a significant improvement in survival rate when subjected to drought stress and then irrigation. Under limited water supply conditions, compared with WT, the photosynthesis and water use efficiency (WUE) of transgenic lines were increased by 39.2% and 28.8%, respectively. Finally, the transgenic lines had 25.5% and 66.4% higher grain yield than the WT under full watering and limited water supply conditions, respectively. Compared with the WT, the agronomic nitrogen use efficiency (NUE) of transgenic lines increased by 25.5% and 66.4% under full watering and limited water supply conditions, and the N recovery efficiency of transgenic lines increased by 29.3% and 50.2%, respectively. The interaction between OsNAR2.1 protein and OsPLDα1 protein was verified by yeast hybrids. After drought treatment, PLDα activity on the plasma membrane of the transgenic line increased 85.0% compared with WT. CONCLUSION: These results indicated that pOsNAR2.1:OsNAR2.1 expression could improve the drought resistance of rice by increasing nitrogen uptake and regulating the expression of OsPLDα1.
Droughts , Gene Expression Regulation, Plant , Oryza , Plant Proteins , Promoter Regions, Genetic , Drought Resistance , Nitrogen/metabolism , Oryza/genetics , Oryza/physiology , Plant Proteins/genetics , Plant Proteins/metabolism , Plants, Genetically Modified
Electrochemical glycerol oxidation (EGO) emerges as a promising route to valorize glycerol, an underutilized byproduct from biodiesel production, into value-added chemicals. This study employed three types of gold (Au) nanocrystals with controlled shapes to elucidate the facet-dependent electrocatalytic behavior in EGO. Octahedral, rhombic dodecahedral, and cubic Au nanocrystals with {111}, {110}, and {100} facets, respectively, were precisely synthesized with uniform size and shape. Rhombic dodecahedra exhibited the lowest onset potential for EGO due to facile AuOH formation, while octahedra showed enhanced electrochemical activity for glycerol oxidation and resistance to poisoning. In-situ FTIR analysis revealed that Au {111} surfaces selectively favored C2 products, whereas Au {100} surfaces promoted C3 product formation, highlighting the significant effect of facet orientation on EGO performance and informing catalyst design.
Transforming polyolefin waste into liquid alkanes through tandem cracking-alkylation reactions catalyzed by Lewis-acid chlorides offers an efficient route for single-step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C-C bonds and forming C-C bonds in alkylation. Here, we show that efficient and selective deconstruction of low-density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline-range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000 g L D P E m o l c a t - 1 h - 1 ${{{\rm g}}_{{\rm L}{\rm D}{\rm P}{\rm E}}{{\rm \ }{\rm m}{\rm o}{\rm l}}_{{\rm c}{\rm a}{\rm t}}^{-1}{{\rm \ }{\rm h}}^{-1}}$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.
Plastic hydrogenolysis is an attractive approach for producing value-added chemicals due to its mild reaction conditions, but controlling product distribution is challenging due to the formation of undesired CH4. This work reports several bimetallic RuM3/CeO2 (M = Fe, Co, Ni) catalysts that shift the product of low-density polyethylene hydrogenolysis toward longer-chain hydrocarbons. These catalysts were characterized by using X-ray absorption fine structure spectroscopy, electron microscopy imaging, and H2 temperature-programmed reduction. The combined catalytic evaluation and characterization results revealed that the product distribution was regulated by the formation of bimetallic alloys. A model compound, n-hexadecane, was selected to further understand the differences in hydrogenolysis over the Ru-based catalysts. Although a longer reaction time shifted the product toward smaller molecules, the bimetallic (RuCo3/CeO2) catalyst limited the further conversion of C2-C5 into CH4. This work highlights the role of bimetallic alloys in tailoring the interaction with hydrocarbons, thereby controlling the product distribution of polymer hydrogenolysis.
Due to their role in controlling global climate change, the selective conversion of C1 molecules such as CH4, CO, and CO2 has attracted widespread attention. Typically, H2O competes with the reactant molecules to adsorb on the active sites and therefore inhibits the reaction or causes catalyst deactivation. However, H2O can also participate in the catalytic conversion of C1 molecules as a reactant or a promoter. Herein, we provide a perspective on recent progress in the mechanistic studies of H2O-mediated conversion of C1 molecules. We aim to provide an in-depth and systematic understanding of H2O as a promoter, a proton-transfer agent, an oxidant, a direct source of hydrogen or oxygen, and its influence on the catalytic activity, selectivity, and stability. We also summarize strategies for modifying catalysts or catalytic microenvironments by chemical or physical means to optimize the positive effects and minimize the negative effects of H2O on the reactions of C1 molecules. Finally, we discuss challenges and opportunities in catalyst design, characterization techniques, and theoretical modeling of the H2O-mediated catalytic conversion of C1 molecules.
We propose a design of the compact high-resolution photonic crystal (PhC) spectrometer with a wide working bandwidth based on both super-prism and local-super-collimation (LSC) effects. The optimizing methods, finding the ideal incident angle and oblique angle of PhC for a wider working bandwidth and ideal incident beam width and PhC size for a certain resolution requirement, are developed. Besides the theoretical work, for the first time, the experiment of such a PhC spectrometer is conducted in the microwave frequency range, and the beam-splitting effects for different frequencies in a wide working bandwidth agree very well with the theoretical predictions. According to the scalability, with the condition to control the deviations in the fabrication processes the design could be extended to optical frequency ranges, e.g., infrared, visible-light, and ultraviolet ranges. The spectrometer in optical frequencies can be implemented on silicon-on-insulator (SOI) chips as a thin-slab structure so that the operating bandwidth can be expanded further through the multi-layer design. Theoretically, the size of the ultra-high-resolution PhC spectrometer in optical frequency ranges based on our design could be two orders smaller than the traditional design.
As a great threat to the normal growth of rice, drought not only restricts the growth of rice, but also affects its yield. Glutathione S-transferases (GSTs) have antioxidant and detoxification functions. In rice, GSTs can not only effectively cope with biological stress, but also play a defense role against abiotic stress. In this study, we selected OsGSTU17, a member gene that was induced by drought, to explore the role of GSTs and analyze their physiological mechanisms that are involved in rice drought tolerance. With the CRISPR/Cas9 knockout system techniques, we obtained two independent mutant lines of osgstu17. After 14 days of drought stress treatment, and then re-supply of the water for 10 days, the survival rate of the osgstu17 mutant lines was significantly reduced compared to the wild-type (WT). Similarly, with the 10% (w/v) PEG6000 hydroponics experiment at the seedling stage, we also found that compared with the WT, the shoot and root biomass of osgstu17 mutant lines decreased significantly. In addition, both the content of the MDA and H2O2, which are toxic to plants, increased in the osgtu17 mutant lines. On the other hand, chlorophyll and proline decreased by about 20%. The activity of catalase and superoxide dismutase, which react with peroxides, also decreased by about 20%. Under drought conditions, compared with the WT, the expressions of the drought stress-related genes OsNAC10, OsDREB2A, OsAP37, OsP5CS1, OsRAB16C, OsPOX1, OsCATA, and OsCATB in the osgtu17 mutant lines were significantly decreased. Finally, we concluded that knocking out OsGSTU17 significantly reduced the drought tolerance of rice; OsGSTU17 could be used as a candidate gene for rice drought-tolerant cultivation. However, the molecular mechanism of OsGSTU17 involved in rice drought resistance needs to be further studied.
ConspectusIn recent years, the simultaneous upgrading of CO2 and ethane has emerged as a promising approach for generating valuable gaseous (CO, H2, and ethylene) and liquid (aromatics and C3 oxygenates) chemicals from the greenhouse gas CO2 and large-reserved shale gas. The key challenges for controlling product selectivity lie in the selective C-H and C-C bond cleavage of ethane with the assistance of CO2. Bimetallic-derived catalysts likely undergo alloying or oxygen-induced segregation under reaction conditions, thus providing diverse types of interfacial sites, e.g., metal/support (M/M'Ox) interface and metal oxide/metal (M'Ox/M) inverse interface, that are beneficial for selective CO2-assisted ethane upgrading. The alloying extent can be initially predicted by cohesive energy and atomic radius (or Wigner-Seitz radius), while the preference for segregation to form the on-top suboxide can be approximated using the work function, electronegativity, and binding strength of adsorbed oxygen. Furthermore, bimetallic-derived catalysts are typically supported on high surface area oxides. Modifying the reducibility and acidity/basicity of the oxide supports and introducing surface defects facilitate CO2 activation and oxygen supplies for ethane activation.Using in situ synchrotron characterization and density functional theory (DFT) calculations, we found that the electronic properties of oxygen species influence the selective cleavage of C-H/C-C bonds in ethane, with electron-deficient oxygen over the metal (or alloy) surface promoting nonselective bond scission to produce syngas and electron-enriched oxygen over the metal oxide/metal interface enhancing selective C-H scission to yield ethylene. We further demonstrate that the preferred structures of the catalyst surfaces, either alloy surfaces or metal oxide/metal inverse interfaces, can be controlled through the appropriate choice of metal combinations and their atomic ratios. Through a comprehensive comparison of experimental results and DFT calculations, the selectivity of C-C/C-H bond scission is correlated with the thermodynamically favorable bimetallic-derived structures (i.e., alloy surfaces or metal oxide/metal inverse interfaces) under reaction conditions over a wide range of bimetallic catalysts. These findings not only offer structural and mechanistic insights into bimetallic-derived catalysts but also provide design principles for selective catalysts for CO2-assisted activation of ethane and other light alkanes. This Account concludes by discussing challenges and opportunities in designing advanced bimetallic-derived catalysts, incorporating new reaction chemistries for other products, employing precise synthesis strategies for well-defined structures with optimized site densities, and leveraging time/spatial/energy-resolved in situ spectroscopy/scattering/microscopy techniques for comprehensive structural analysis. The research methodologies established here are helpful for the investigation of dynamic alloy and interfacial structures and should inspire more efforts toward the simultaneous upgrading of CO2 and shale gas.
Electroreduction of carbon dioxide (CO2) or carbon monoxide (CO) toward C2+ hydrocarbons such as ethylene, ethanol, acetate and propanol represents a promising approach toward carbon-negative electrosynthesis of chemicals. Fundamental understanding of the carbonâcarbon (C-C) coupling mechanisms in these electrocatalytic processes is the key to the design and development of electrochemical systems at high energy and carbon conversion efficiencies. Here, we report the investigation of CO electreduction on single-atom copper (Cu) electrocatalysts. Atomically dispersed Cu is coordinated on a carbon nitride substrate to form high-density copperânitrogen moieties. Chemisorption, electrocatalytic, and computational studies are combined to probe the catalytic mechanisms. Unlike the Langmuir-Hinshelwood mechanism known for copper metal surfaces, the confinement of CO adsorption on the single-copper-atom sites enables an Eley-Rideal type of C-C coupling between adsorbed (*CO) and gaseous [CO(g)] carbon moxide molecules. The isolated Cu sites also selectively stabilize the key reaction intermediates determining the bifurcation of reaction pathways toward different C2+ products.
One possible solution to closing the loop on carbon emissions is using CO2 as the carbon source to generate high-value, multicarbon products. In this Perspective, we describe four tandem reaction strategies for converting CO2 into C3 oxygenated hydrocarbon products (i.e., propanal and 1-propanol), using either ethane or water as the hydrogen source: (1) thermocatalytic CO2-assisted dehydrogenation and reforming of ethane to ethylene, CO, and H2, followed by heterogeneous hydroformylation, (2) one-pot conversion of CO2 and ethane using plasma-activated reactions in combination with thermocatalysis, (3) electrochemical CO2 reduction to ethylene, CO, and H2, followed by thermocatalytic hydroformylation, and (4) electrochemical CO2 reduction to CO, followed by electrochemical CO reduction to C3 oxygenates. We discuss the proof-of-concept results and key challenges for each tandem scheme, and we conduct a comparative analysis of the energy costs and prospects for net CO2 reduction. The use of tandem reaction systems can provide an alternative approach to traditional catalytic processes, and these concepts can be further extended to other chemical reactions and products, thereby opening new opportunities for innovative CO2 utilization technologies.
Magnesium (Mg) is an essential element for plant growth and development. Rice is an important food crop in the world, but there are few studies on the uptake and translocation of Mg2+ in rice. We used a multi-parent advanced generation inter-cross (MAGIC) population constructed using four parental lines and genotyped by a 55 K rice SNP array for association analysis to locate QTLs related to Mg2+ uptake and translocation in rice at the seedling stage. Four QTLs (qRMg1, qRMg2, qRMg7 and qRMg8) were detected for the root Mg2+ concentration, which explained 11.45-13.08% of the phenotypic variation. The Mg2+ transporter gene, OsMGT1, was within the region of qRMg1. Three QTLs (qSMg3, qSMg7 and qSMg10) were detected for the shoot Mg2+ concentration, which explained 4.30-5.46% of the phenotypic variation. Two QTLs (qTrMg3 and qTrMg8) were found to affect the translocation of Mg2+ from the roots to the shoots, and explained 10.91% and 9.63% of phenotypic variation. qSMg3 and qTrMg3 might be the same, since they are very close to each other on chromosome 3. Analysis of candidate genes in the region of qSMg3 and qTrMg3 through qRT-PCR, complementation assay in the yeast Mg2+ transport-defective mutant CM66, and sequence analysis of the parental lines suggested that LOC_Os03g04360 may play important roles in Mg2+ uptake, translocation and accumulation in rice. Overexpression of LOC_Os03g04360 can significantly increase the Mg2+ concentration in rice seedlings, especially under the condition of low Mg2+ supply.
