[Progress in enrichment methods for protein N-phosphorylation].

Protein phosphorylation is one of the most common and important post-translational modifications that regulates almost all life processes. In particular, protein phosphorylation regulates the development of major diseases such as tumors, neurodegenerative diseases, and diabetes. For example, excessive phosphorylation of Tau protein can cause neurofibrillary tangles, leading to Alzheimer's disease. Therefore, large-scale methods for identifying protein phosphorylation must be developed. Rapid developmentin efficient enrichment methods and biological mass spectrometry technologies have enabled the large-scale identification of low-abundance protein O-phosphorylation modifications in, allowing for a more thorough study of their biological functions. The N-phosphorylation modifications that occur on the side-chain amino groups of histidine, arginine, and lysine have recently received increased attention. For example, the biological function of histidine phosphorylation in prokaryotes has been well studied; this type of modification regulates signal transduction and sugar metabolism. Two mammalian pHis kinases (NME1 and NME2) and three pHis phosphatases (PHPT1, LHPP, and PGAM5) have been successfully identified using various biological methods. N-Phosphorylation is involved in multiple biological processes, and its functions cannot be ignored. However, N-phosphorylation is unstable under acidic and thermal conditions owing to the poor chemical stability of the P-N bond. Unfortunately, the current O-phosphorylation enrichment method, which relies on acidic conditions, is unsuitable for N-phosphorylation enrichment, resulting in a serious lag in the large-scale identification of protein N-phosphorylation. The lack of enrichment methods has also seriously hindered studies on the biological functions of N-phosphorylation. Therefore, the development of efficient enrichment methods that target protein N-phosphorylation is an urgent undertaking. Research on N-phosphorylation proteome enrichment methods is limited, hindering functional research. Thus, summarizing such methods is necessary to promote further functional research. This article introduces the structural characteristics and reported biological functions of protein N-phosphorylation, reviews the protein N-phosphorylation modification enrichment methods developed over the past two decades, and analyzes the advantages and disadvantages of each method. In this study, both antibody-based and nonantibody-dependent methods are described in detail. Owing to the stability of the molecular structure of histidine, the antibody method is currently limited to histidine phosphorylation enrichment research. Future studies will focus on the development of new enrichment ligands. Moreover, research on ligands will promote studies on other nonconventional phosphorylation targets, such as two acyl-phosphates (pAsp, pGlu) and S-phosphate (pCys). In summary, this review provides a detailed analysis of the history and development directions of N-phosphorylation enrichment methods.

In-situ construction of iron-modified nickel nanoparticles assisted by hexamethylenetetramine with the internal and external collaboration for highly selective electrocatalytic carbon dioxide reduction.

Carbon dioxide (CO2) electroreduction provides a sustainable route for realizing carbon neutrality and energy supply. Up to now, challenges remain in employing abundant and inexpensive nickel materials as candidates for CO2 reduction due to their low activity and favorable hydrogen evolution. Here, the representative iron-modified nickel nanoparticles embedded in nitrogen-doped carbon (Ni1-Fe0.125-NC) with the porous botryoid morphology were successfully developed. Hexamethylenetetramine is used as nitrogen-doped carbon source. The collaboration of internal lattice expansion with electron effect and external confinement effect with size effect endows the significant enhancement in electrocatalytic CO2 reduction. The optimized Ni1-Fe0.125-NC exhibits broad potential ranges for continuous carbon monoxide (CO) production. A superb CO Faradaic efficiency (FECO) of 85.0 % realized at -1.1 V maintains a longtime durability over 35 h, which exceeds many state-of-the-art metal catalysts. Theoretical calculations further confirm that electron redistribution promotes the desorption of CO in the process for favorable CO production. This work opens a new avenue to design efficient nickel-based materials by considering the intrinsic structure and external confinement for CO2 reduction.

Removal mechanism of Pb(ii) from soil by biochar-supported nanoscale zero-valent iron composite materials.

As an adsorbent, biochar has a highly porous structure and strong adsorption capacity, and can effectively purify the environment. In response to the increasingly serious problem of heavy metal pollution in water, this study used nano zero valent iron and rice husk biochar to prepare a new type of magnetic sheet-like biochar loaded nano zero valent iron (BC-nZVI) composite material through rheological phase reaction, showing remarkable advantages such as low cost, easy preparation, and superior environmental remediation effect. The physical and chemical properties and structure of the material were extensively characterized using various methods such as HRTEM, XPS, FESEM, EDS, XRD, FTIR, and RAMAN. Concurrently, batch experiments were undertaken to assess the removal efficiency of Pb(ii) by BC-nZVI, with investigations into the influence of pH value, temperature, soil water ratio, and initial concentration of heavy metal ion solution on its removal efficiency. The results indicate that the removal of Pb(ii) by BC-nZVI reaches an equilibrium state after around 120 minutes. Under the conditions of pH 6, temperature 20 °C, soil water ratio 1 : 5, and BC-nZVI dosage of 1 g L-1, BC-nZVI can reduce the Pb(ii) content in wastewater with an initial concentration of 30 mg L-1 to trace levels, and the treatment time is about 120 minutes. The analysis of adsorption kinetics and isotherms indicates that the adsorption process of Pb(ii) by BC-nZVI adheres to the quasi-second-order kinetic model and Langmuir model, suggesting a chemical adsorption process. Thermodynamic findings reveal that the adsorption of Pb(ii) by BC-nZVI is spontaneous. Furthermore, BC-nZVI primarily accumulates Pb(ii) through adsorption co-precipitation. BC-nZVI serves as an eco-friendly, cost-effective, and highly efficient adsorbent, showing promising capabilities in mitigating Pb(ii) heavy metal pollution. Its recoverability and reusability facilitated by an external magnetic field make it advantageous for remediating and treating lead-contaminated sites.

Insight into the Critical Role of Oxygen Vacancies and V=O Bonds Length in V2O5 for Advanced Zinc Ion Storage.

Due to the larger sizes and stronger positive polarity of Zn2+ than dominant univalent ions, Zn2+ sluggish diffusion within V2O5 host electrodes is an essential issue in developing aqueous zinc-ion batteries (ZIBs) of higher energy densities. Herein, a high-performance V2O5 cathode was developed through subtly synthesizing and tuning V2O5 with oxygen vacancies-enriched and elongated apical V=O1 bond by altering the gradient concentration of hydrazine hydrate in the gas-solid reaction system. This strategy can enhance both intrinsic and extrinsic conductivity to a large extent. The electrochemical testing demonstrated the oxygen vacancies-enriched and elongated apical V=O1 bond can not only increase the intrinsic electronic conductivity of V2O5, but also induce additional pseudocapacitance to enhance the Zn2+ diffusion kinetics. We used infrared spectroscopy and Raman spectroscopy to characterize the change in the bond length structure of V2O5. Simultaneously, the long-term cyclability (capacity retention of 76.9 % after 1200 cycles at 4.0 A g-1) and rate capabilities (218 mAh g-1 at 4.0 A g-1) are promoted as well. We believe that our work might shed light on the bond length engineering of V2O5 and provide insights for the reasonable designing of novel cathodes for practical rechargeable ZIBs.

Efficient CO2 Capture and Separation in MOFs: Effect from Isoreticular Double Interpenetration.

Severe CO2 emissions has posed an increasingly alarming threat, motivating the development of efficient CO2 capture materials, one of the key parts of carbon capture, utilization, and storage (CCUS). In this study, a series of metal-organic frameworks (MOFs) named Sc-X (X = S, M, L) were constructed inspired by recorded MOFs, Zn-BPZ-SA and MFU-4l-Li. The corresponding isoreticular double-interpenetrating MOFs (Sc-X-IDI) were subsequently constructed via the introduction of isoreticular double interpenetration. Grand canonical Monte Carlo (GCMC) simulations were adopted at 298 K and 0.1-1.0 bar to comprehensively evaluate the CO2 capture and separation performances in Sc-X and Sc-X-IDI, with gas distribution, isothermal adsorption heat (Qst), and van der Waals (vdW)/Coulomb interactions. It is showed that isoreticular double interpenetration significantly improved the interactions between adsorbed gases and frameworks by precisely modulating pore sizes, particularly observed in Sc-M and Sc-M-IDI. Specifically, the Qst and Coulomb interactions exhibited a substantial increase, rising from 28.38 and 22.19 kJ mol-1 in Sc-M to 43.52 and 38.04 kJ mol-1 in Sc-M-IDI, respectively, at 298 K and 1.0 bar. Besides, the selectivity of CO2 over CH4/N2 was enhanced from 55.36/107.28 in Sc-M to 3308.61/7021.48 in Sc-M-IDI. However, the CO2 capture capacity is significantly influenced by the pore size. Sc-M, with a favorable pore size, exhibits the highest capture capacity of 15.86 mmol g-1 at 298 K and 1.0 bar. This study elucidated the impact of isoreticular double interpenetration on the CO2 capture performance in MOFs.

N,S coordination in Ni single-atom catalyst promoting CO2RR towards HCOOH.

Carbon-based single atom catalysts (SACs) are attracting extensive attention in the CO2 reduction reaction (CO2RR) due to their maximal atomic utilization, easily regulated active center and high catalytic activity, in which the coordination environment plays a crucial role in the intrinsic catalytic activity. Taking NiN4 as an example, this study reveals that the introduction of different numbers of S atoms into N coordination (Ni-NxS4-x (x = 1-4)) results in outstanding structural stability and catalytic activity. Owing to the additional orbitals around -1.60 eV and abundant Ni dxz, dyz, dx2, and dz2 orbital occupation after S substitution, N,S coordination can effectively facilitate the protonation of adsorbed intermediates and thus accelerate the overall CO2RR. The CO2RR mechanisms for CO and HCOOH generation via two-electron pathways are systematically elucidated on NiN4, NiN3S1 and NiN2S2. NiN2S2 yields HCOOH as the most favorable product with a limiting potential of -0.24 V, surpassing NiN4 (-1.14 V) and NiN3S1 (-0.50 V), which indicates that the different S-atom substitution of NiN4 has considerable influence on the CO2RR performance. This work highlights NiN2S2 as a high-performance CO2RR catalyst to produce HCOOH, and demonstrates that N,S coordination is an effective strategy to regulate the performance of atomically dispersed electrocatalysts.

Improving rice nitrogen-use efficiency by modulating a novel monouniquitination machinery for optimal root plasticity response to nitrogen.

Plant nitrogen (N)-use efficiency (NUE) is largely determined by the ability of root to take up external N sources, whose availability and distribution in turn trigger the modification of root system architecture (RSA) for N foraging. Therefore, improving N-responsive reshaping of RSA for optimal N absorption is a major target for developing crops with high NUE. In this study, we identified RNR10 (REGULATOR OF N-RESPONSIVE RSA ON CHROMOSOME 10) as the causal gene that underlies the significantly different root developmental plasticity in response to changes in N level exhibited by the indica (Xian) and japonica (Geng) subspecies of rice. RNR10 encodes an F-box protein that interacts with a negative regulator of auxin biosynthesis, DNR1 (DULL NITROGEN RESPONSE1). Interestingly, RNR10 monoubiquitinates DNR1 and inhibits its degradation, thus antagonizing auxin accumulation, which results in reduced root responsivity to N and nitrate (NO3-) uptake. Therefore, modulating the RNR10-DNR1-auxin module provides a novel strategy for coordinating a desirable RSA and enhanced N acquisition for future sustainable agriculture.

Bioinspired trimesic acid anchored electrocatalysts with unique static and dynamic compatibility for enhanced water oxidation.

Layered double hydroxides are promising candidates for the electrocatalytic oxygen evolution reaction. Unfortunately, their catalytic kinetics and long-term stabilities are far from satisfactory compared to those of rare metals. Here, we investigate the durability of nickel-iron layered double hydroxides and show that ablation of the lamellar structure due to metal dissolution is the cause of the decreased stability. Inspired by the amino acid residues in photosystem II, we report a strategy using trimesic acid anchors to prepare the subsize nickel-iron layered double hydroxides with kinetics, activity and stability superior to those of commercial catalysts. Fundamental investigations through operando spectroscopy and theoretical calculations reveal that the superaerophobic surface facilitates prompt release of the generated O2 bubbles, and protects the structure of the catalyst. Coupling between the metals and coordinated carboxylates via C‒O‒Fe bonding prevents dissolution of the metal species, which stabilizes the electronic structure by static coordination. In addition, the uncoordinated carboxylates formed by dynamic evolution during oxygen evolution reaction serve as proton ferries to accelerate the oxygen evolution reaction kinetics. This work offers a promising way to achieve breakthroughs in oxygen evolution reaction stability and dynamic performance by introducing functional ligands with static and dynamic compatibilities.

Cost-effective core@shell structured zero-valent iron nanoparticles @ magnetic (nZVI@Fe3O4) for Cr(vi) removal from aqueous solutions: preparation by disproportionation of Fe(ii).

Nanoscale zero-valent iron (nZVI) and its composites are known for their excellent ability to remove Cr(vi), but their preparation can be expensive due to the reduction processes. This study presents a cost-effective method to prepare core@shell structured nZVI@Fe3O4 nanocomposites using a novel Fe(ii) disproportionation reaction. The nZVI@Fe3O4 was thoroughly characterized using various techniques, including FESEM, HRTEM, EDS, XPS, XRD, FTIR, and VSM. Batch experiments were performed to evaluate the removal efficiency of nZVI@Fe3O4 in eliminating Cr(vi) ions from aqueous solutions, while classical models were employed to investigate the influencing factors associated with the removal process. The results showed that a 0.7 mg per ml NaOH solution reacted with Fe(ii) at 150 °C for 0.5 h could be used to prepare nZVI@Fe3O4 composites efficiently and inexpensively. nZVI@Fe3O4 was able to remove more than 99% of Cr(vi) from both simulated Cr(vi) solutions and real electroplating wastewater, and the recovery and preparation could be easily performed using external magnets to separate it from the solution. At pH 6.0, the maximum adsorption capacity (qmax) for Cr(vi) reached 58.67 mg g-1. The reaction mechanism was discussed from the perspective of electron transfer. Overall, the results suggest that nZVI@Fe3O4, an efficient adsorbent prepared using an environmentally friendly and inexpensive Fe(ii) disproportionation reaction, is a promising option for the treatment of Cr(vi) from industrial wastewater and other contaminated water sources.

Enhanced CO2 capture in partially interpenetrated MOFs: Synergistic effects from functional group, pore size, and steric-hindrance.

Excessive CO2 emissions have contributed to global environmental issues, driving the development of CO2 capture adsorbents. Among various candidates, metal-organic frameworks (MOFs) are considered the most promising due to their unique microporous structure. Herein, a series of partially interpenetrated MOFs named UPC-XX were built to investigate the continuous enhancement in CO2 capture performance via synergistic effects from functional group, pore size, and steric-hindrance using theoretical calculations. It's showed that the introduction of functional groups improved the structure polarity and created more adsorption sites, thus, enhanced CO2 capture capacity. The pore size modification augments the exposure of adsorption sites to mitigate the negative impact of pore space and surface area reduction caused by the introduction of functional groups, thereby further increasing the CO2 capture capacity. The steric-hindrance effect optimized the adsorption sites distribution, which hasn't been considered in the previous two regulation strategies, thus, further increased the CO2 capture capacity. The results underscore UPC-MOFs as outstanding adsorbent materials, among the UPC-MOFs, UPC-OSO3-steric exhibited the highest CO2 capture capacity of 12.69 mmol/g with selectivities of 1142.41 (CO2 over N2) and 507.42 (CO2 over CH4) at 1.0 bar, 298 K. And the synergistic effect mechanisms of functional group, structure size, and steric hindrance were elucidated through theoretical calculations analyzing pore characteristics, gas distribution, isosteric heat, and van der Waals/Coulomb interactions.

Two-dimensional MBene: a comparable catalyst to MXene for effective CO2RR towards C1 products.

Electrochemical CO2 reduction reaction (CO2RR) to high-value-added products is one of the most promising strategies for mitigating the greenhouse effect and energy shortage. Two-dimensional (2D) MXene materials are regarded as promising catalysts for electrocatalysis, and the boron-analogs of MXenes, 2D transition metal borides (MBenes), may exhibit superior CO2RR performance owing to their unique electronic properties. Herein, a novel 2D transition metal boride, MoB, is theoretically evaluated as a potential catalyst for the CO2RR by comparing it with traditional Mo2C. MoB shows metallic nature and exhibits excellent electrical conductivity. MoB can effectively activate CO2 with a larger interaction energy of -3.64 eV than that of Mo2C. Both density of states and charge difference density reveal a significant charge transfer from MoB to CO2. MoB shows higher catalytic selectivity due to its inhibited hydrogen evolution reaction and low reaction energy for the CO2RR. At potentials more negative than -0.62 V, the CO2RR on MoB becomes a high-throughput reaction process towards CH4. This work discovered that MoB exhibited comparable CO2RR performance to Mo2C and forecasted MBenes as promising catalysts for electrocatalysis.

Constructing N,S and N,P Co-Coordination in Fe Single-Atom Catalyst for High-Performance Oxygen Redox Reaction.

Single-atom catalysts (SACs) are promising electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), in which the coordination environment plays a crucial role in activating the intrinsic activity of the central metal. Taking the FeN4 SAC as a probe, this work investigates the effect of introducing S or P atoms into N coordination (FeSx N4-x and FePx N4-x (x=1-4)) on the electronic structure optimization of Fe center and its catalytic performance. Attributing to the optimal Fe 3d orbitals, FePN3 can effectively activate O2 and promote ORR with a low overpotential of 0.29 V, surpassing FeN4 and most reported catalysts. FeSN3 is beneficial to H2 O activation and OER, proceeding with an overpotential of 0.68 V, which is superior to FeN4 . Both FePN3 and FeSN3 exhibit outstanding thermodynamic and electrochemical stability with negative formation energies and positive dissolution potentials. Hence, the N,P and N,S co-coordination might provide better catalytic environment than regular N coordination for SACs in ORR and OER. This work demonstrates FePN3 /FeSN3 as high-performance ORR/OER catalysts and highlights N,P and N,S co-coordination regulation as an effective approach to fine tune high atomically dispersed electrocatalysts.

Precise electronic structure modulation on MXene-based single atom catalysts for high-performance electrocatalytic CO2 reduction reaction: A first-principle study.

Electrocatalytic CO2 reduction reaction (CO2RR) to CO is a logical approach to achieve a carbon-neutral cycle. In this work, a series of Ti2CO2 and O vacancy containing Ti2CO2 MXene-based transition metal (TM) single atom catalysts (SACs), including TM-Ti2CO2 and TM-Ov-Ti2CO2, are explored for high-performance CO2RR. Sc/Ti/V/Cr-Ti2CO2 and Ni-Ov-Ti2CO2 are screened out with limiting potential (UL) more positive than -0.50 V. Ni-Ov-Ti2CO2 is a candidate catalyst for CO2RR to CO, considering its activity with UL of -0.27 eV, and the selectivity relevant to hydrogen evolution reaction and HCOOH production. Meanwhile, a novel activity descriptor of TM-Ti-O group valence state is proposed according to that TMs work in synergy with coordinated Ti and O atoms and a level of around 0.64 e- benefits to CO2RR. This work highlights oxygen vacancy containing Ti2CO2-based Ni SAC as a promising catalyst for CO2RR, and provides a feasible electronic structure design principle for guiding the design of MXene-based SACs for CO2RR.

Effects of Shale Pore Size and Connectivity on scCO2 Enhanced Oil Recovery: A Molecular Dynamics Simulation Investigation.

The differences in pore width distributions and connectivity of shale reservoirs have significant influences on supercritical carbon dioxide (scCO2)-enhanced oil recovery (CO2 EOR) in shale. Herein, the molecular dynamics simulation was adopted to investigate the microscopic mechanism of CO2 EOR in the shale nanopores with different pore size width distributions and pore connectivity. The results show that the pore connectivity has significant effects on the oil displacement, and the recovery efficiency is ordered as: connected pore > double pore > single pore for the 3 nm pore, which are 91.32, 74.43, and 65.93%, respectively. Therefore, the increase in pore connectivity can significantly improve the recovery efficiency of the small pore of the connected pore system. For the shale reservoirs with different pore width distributions, the oil recovery rate of large pores is generally higher than that of small pores. In addition, the displacement of oil in the small pore of the double pore system is accelerated due to the pushing effect of the discharge fluid from the large pore. The results furnish a certain theoretical support for the research of the microscopic mechanism of CO2 EOR in the shale pore with different pore width distributions and connectivity and the exploit of shale oil.

Graphdiyne supported Ag-Cu tandem catalytic scheme for electrocatalytic reduction of CO2 to C2+ products.

The electrochemical CO2 reduction reaction (CO2RR) to added-value C2+ products is a worthy way to effectively reduce CO2 levels in the atmosphere. Cu nanomaterials have been proposed as efficient CO2RR catalysts for producing C2+ products; however, the difficulties in controlling their efficiency and selectivity hinder their applications. Herein, we propose a simple routine to construct a graphdiyne (GDY) supported Ag-Cu nanocluster as a C2+ product-selective electrocatalyst and optimize the composition by electrochemical performance screening. The synthesized Ag-Cu nanoclusters are uniformly distributed on the surface of GDY with particle sizes constricted to 3.7 nm due to the strong diyne-Cu interaction. Compared to Cu/GDY, Ag-Cu/GDY tandem schemes exhibited superior CO2RR to C2+ performance with a Faraday efficiency (FE) of up to 55.1% and a current density of 48.6 mA cm-2 which remain stable for more than 33 hours. Theoretical calculations show that the adsorption energy of CO is much higher on Cu (-1.066 eV) than on Ag (-0.615 eV), thus promoting the drift of *CO from Ag to Cu. Moreover, the calculations indicate that the key C-C coupling reaction of *CO with *COH is more favored on Ag-Cu/GDY than on the original Cu/GDY which contributes to the formation of C2+ products. Our findings shed light on a new strategy of combining a GDY support with a tandem catalytic scheme for developing new CO2RR catalysts with superior selectivity and activity for C2+ products.

Two birds with one stone: large catalytic areas and abundant nitrogen sites inspired by fluorine doping contributing to CO2RR activity and selectivity.

Electroreduction of CO2 based on metal-free carbon catalysts is an attractive approach for useful products. However, it remains a great chemical challenge due to its unsatisfactory activity and poor selectivity. Here, we report a successful case to greatly improve CO2-to-CO conversion on carbon black (CB) and nitrogen-doped carbon black (N-CB). By introducing fluorine, the faradaic efficiency of CO was increased from 12.8% (CB) and 50.8% (N-CB) to 93.1% (nitrogen and fluorine co-doped carbon black, N,F-CB) at -0.7 V. A partial current density of 4.19 mA cm-2 remained durable for about 23 h. The superiority of N,F-CB can be attributed to its large catalytic areas and abundant N active sites inspired by fluorine doping. Specifically, the fluorine precursor of polyvinylidene fluoride (PVDF) firstly performs as a nitrogen fixator, protecting the catalyst from more nitrogen escaping during the carbonization treatment. The number of nitrogen sites is about 4.4 times higher than it is for the N-CB. Meanwhile, PVDF as the area extender significantly improves the catalytic area; the specific surface area and the ECSA of N,F-CB are 8.7 and 6.9 times higher than that of CB. This work provides an insight into how heteroatoms can manipulate catalytic activity and selectivity through the catalytic area of carbon materials with more active sites.

Interlayer Expansion in a Layered Metal-Organic Framework Enhances CO2 Capture and CO2 /N2 Separation.

Developing efficient CO2 adsorbent materials and technologies is significant to reduce the increasing greenhouse gases concentration in the atmosphere. Herein, a layered MOF with a porous kagomé lattice (kgm), which owned three phases (kgm-1, kgm-2, and kgm-3) via interlayer expansion, was evaluated as a promising CO2 capture and separation material by using grand canonical Monte Carlo simulations. Results showed that the interlayer expansion provided additional pore volume, which played a considerable role in CO2 adsorption and separation. The CO2 adsorption capacity and CO2 /N2 selectivity followed the sequence kgm-3>kgm-2>kgm-1, and kgm-3 exhibited an excellent CO2 adsorption capacity of 8.7 mmol g-1 at 1 bar with a CO2 /N2 selectivity of 130.3 at 20 bar and 298 K. Gas distribution analysis showed that CO2 and N2 are adsorbed only in the channels in kgm-1, whereas they could be adsorbed between layers in kgm-2 and kgm-3 due to the interlayer expansion. The adsorption heat and interactions between CO2 and frameworks were analyzed to elucidate the effect of interlayer expansion. Results of this work highlighted that appropriate interlayer expansion can be an effective approach for framework adsorbents to improve CO2 capture ability and separation performance at the same time.

Surface-Plasmon-Mediated Alloying for Monodisperse Au-Ag Alloy Nanoparticles in Liquid.

Plasmonic noble-metal nanoparticles with broadly tunable optical properties and catalytically active surfaces offer a unique opportunity for photochemistry. Resonant optical excitation of surface-plasmon generates high-energy hot carriers, which can participate in photochemical reactions. Although the surface-plasmon-driven catalysis on molecules has been extensively studied, surface-plasmon-mediated synthesis of bimetallic nanomaterials is less reported. Herein, we perform a detailed investigation on the formation mechanism and colloidal stability of monodisperse Au-Ag alloy nanoparticles synthesized through irradiating the intermixture of Au nanochains and AgNO3 solution with a nanosecond pulsed laser. It is revealed that the Ag atoms can be extracted from AgNO3 solution by surface-plasmon-generated hot electrons and alloy with Au atoms. Particularly, the obtained Au-Ag alloy nanoparticles without any surfactants or ligands exhibit superior stability that is confirmed by experiments as well as DLVO-based theoretical simulation. Our work would provide novel insights into the synthesis of potentially useful bimetallic nanoparticles via surface-plasmon-medicated alloying.

Molecular Dynamics Insight into the CO2 Flooding Mechanism in Wedge-Shaped Pores.

Because of the growing demand for energy, oil extraction under complicated geological conditions is increasing. Herein, oil displacement by CO2 in wedge-shaped pores was investigated by molecular dynamics simulation. The results showed that, for both single and double wedge-shaped models, pore Ⅱ (pore size from 3 to 8 nm) exhibited a better CO2 flooding ability than pore Ⅰ (pore size from 8 to 3 nm). Compared with slit-shaped pores (3 and 8 nm), the overall oil displacement efficiency followed the sequence of 8 nm > double pore Ⅱ > single pore Ⅱ > 3 nm > double pore Ⅰ > single pore Ⅰ, which confirmed that the exits of the wedge-shaped pores had determinant effects on CO2 enhanced oil recovery over their entrances. "Oil/CO2 inter-pore migration" and "siphoning" phenomena occurred in wedge-shaped double pores by comparing the volumes of oil/CO2 and the center of mass. The results of the interaction and radial distribution function analyses indicate that the wide inlet and outlet had a larger CO2−oil contact surface, better phase miscibility, higher interaction, and faster displacement. These findings clarify the CO2 flooding mechanisms in wedge-shaped pores and provide a scientific basis for the practical applications of CO2 flooding.

Theoretical Investigation of the Fusion Process of Mono-Cages to Tri-Cages with CH4/C2H6 Guest Molecules in sI Hydrates.

Owing to a stable and porous cage structure, natural gas hydrates can store abundant methane and serve as a potentially natural gas resource. However, the microscopic mechanism of how hydrate crystalline grows has not been fully explored, especially for the structure containing different guest molecules. Hence, we adopt density functional theory (DFT) to investigate the fusion process of structure I hydrates with CH4/C2H6 guest molecules from mono-cages to triple-cages. We find that the volume of guest molecules affects the stabilities of large (51262, L) and small (512, s) cages, which are prone to capture C2H6 and CH4, respectively. Mixed double cages (small cage and large cage) with the mixed guest molecules have the highest stability and fusion energy. The triangular triple cages exhibit superior stability because of the three shared faces, and the triangular mixed triple cages (large-small-large) structure with the mixed guest molecules shows the highest stability and fusion energy in the triple-cage fusion process. These results can provide theoretical insights into the growth mechanism of hydrates with other mono/mixed guest molecules for further development and application of these substances.