Boosting photo-thermal co-catalysis CO2 methanation by tuning interface electron transfer via Mott-Schottky heterojunction effect.

Photo-thermal co-catalytic reduction of CO2 to synthesize value-added chemicals presents a promising approach to addressing environmental issues. Nevertheless, traditional catalysts exhibit low light utilization efficiency, leading to the generation of a reduced number of electron-hole pairs and rapid recombination, thereby limiting catalytic performance enhancement. Herein, a Mott-Schottky heterojunction catalyst was developed by incorporating nitrogen-doped carbon coated TiO2 supported nickel (Ni) nanometallic particles (Ni/x-TiO2@NC). The optimal Ni/0.5-TiO2@NC sample displayed a conversion rate of 71.6 % and a methane (CH4) production rate of 65.3 mmol/(gcat·h) during photo-thermal co-catalytic CO2 methanation under full-spectrum illumination, with a CH4 selectivity exceeding 99.6 %. The catalyst demonstrates good stability as it shows no decay after two reaction cycles. The Mott-Schottky heterojunction catalysts display excellent efficiency in separating photo-generated electron-hole pairs and elevate the catalysts' temperature, thus accelerating the reaction rate. The in-situ experiments revealed that light-induced electron transfer effectively facilitates H2 dissociation and enhances surface defects, thereby promoting CO2 adsorption. This study introduces a novel approach for developing photo-thermal catalysts for CO2 reduction, aiming to enhance solar energy utilization and facilitate interface electron transfer.

Highly Dispersed Mn-Doped Ceria Supported on N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Reaction.

The weak adsorption of oxygen on transition metal oxide catalysts limits the improvement of their electrocatalytic oxygen reduction reaction (ORR) performance. Herein, a dopamine-assisted method is developed to prepare Mn-doped ceria supported on nitrogen-doped carbon nanotubes (Mn-Ce-NCNTs). The morphology, dispersion of Mn-doped ceria, composition, and oxygen vacancies of the as-prepared catalysts were analyzed using various technologies. The results show that Mn-doped ceria was formed and highly dispersed on NCNTs, on which oxygen vacancies are abundant. The as-prepared Mn-Ce-NCNTs exhibit a high ORR performance, on which the average electron transfer number is 3.86 and the current density is 24.4% higher than that of commercial 20 wt % Pt/C. The peak power density of Mn-Ce-NCNTs is 68.1 mW cm-2 at the current density of 138.9 mA cm-2 for a Zn-air battery, which is close to that of 20 wt % Pt/C (69.4 mW cm-2 at 106.1 mA cm-2). Density functional theory (DFT) calculations show that the oxygen vacancy formation energies of Mn-doped CeO2(111) and pure CeO2(111) are -0.55 and 2.14 eV, respectively. Meanwhile, compared with undoped CeO2(111) (-0.02 eV), Mn-doped CeO2(111) easily adsorbs oxygen with the oxygen adsorption energy of only -0.68 eV. This work provides insights into the synergetic effect of Mn-doped ceria for facilitating oxygen adsorption and enhancing ORR performance.

The impact of sustainable development planning on urban ecological resilience in resource-based cities: evidence from China.

Enhancing resource cities' resilience and advancing their sustainable development are imperatives, particularly in light of the "dual-carbon" agenda. Double-difference and spatial double-difference models are developed based on the panel data of 281 Chinese cities from 2005 to 2020 to investigate the effects of implementing the National Plan for the Sustainable Development of Resource-Based Cities on the level of ecological resilience in Chinese cities. This paper found that the National Sustainable Development Plan for Resource-Based Cities significantly improves the ecological resilience level of Chinese cities, and the findings are robust. The impacts of implementing the Plan on the ecological resilience of cities of different growth types, regions, and resource types are heterogeneous. Further study finds a spatial spillover effect of implementing the Plan on the ecological resilience of cities, which can improve the ecological resilience level of neighboring cities through spillover effects while improving the ecological resilience level of cities in the region. Based on these new findings, this study provides some policy implications for better advancing sustainable urban development.

Isomorphous Substitution of Organic Cage Crystal by Pd Nanoclusters for Selective Hydrogenation.

For supporting active metal, the cavity confinement and mass transfer facilitation lie not in one sack, a trade-off between high activity and good stability of the catalyst is present. Porous organic cages (POCs) are expected to break the trade-off when metal particles are properly loaded. Herein, three organic cages (CC3, RCC3, and FT-RCC3) are employed to support Pd nanoclusters for catalytic hydrogenation. Subnanometer Pd clusters locate differently in different cage frameworks by using the same reverse double-solvents approach. Compared with those encapsulated in the intrinsic cavity of RCC3 and anchored on the outer surface of CC3, the Pd nanoclusters orderly assembled in FT-RCC3 crystal via isomorphous substitution exhibit superior activity, high selectivity, and good stability for semi-hydrogenation of phenylacetylene. Isomorphous substitution of FT-RCC3 crystal by Pd nanoclusters is originated from high crystallization capacity of FT-RCC3 and specific interaction of each Pd nanocluster with four cage windows. Both confinement function and H2 accumulation capacity of FT-RCC3 are fully utilized to support active Pd nanoclusters for efficient selective hydrogenation. The present results provide a new perspective to the heterogeneous catalysis field in terms of crystalizing metal nanoclusters in POC framework and outside the cage for making the best use of both parts.

Effectively removing the homodimer in bispecific antibodies by weak partitioning mode of anion exchange chromatography.

Small amounts of by-products are nevertheless created during the recombinant production of IgG-like bispecific antibodies due to imbalanced chain expression and improper chain pairing, despite the employment of molecular strategy techniques to promote accurate pairing. Among them, homodimers represent the species that are more difficult to remove due to their physical and chemical properties being similar to the target antibody. Homodimer by-products are always produced even though various technologies can significantly increase the expression of heterodimers, so a robust purification process to recover high-purity heterodimers is required. Most of the chromatography methods commonly adopt the bind-and-elute mode or two-step to separate homodimers, which has numerous drawbacks such as prolonged process times and limited dynamic binding capacity. Flow-through mode of anion exchange is a frequently-used polishing step for antibodies, but it is typically regarded as being more effective for host-cell protein or host-cell DNA removal rather than other product-related impurities such as homodimers and aggregates. This paper demonstrated that single-step anion exchange chromatography allows high capacity and effective clearance of the homodimer byproduct to be simultaneously achieved, suggesting that weak partitioning was a better polishing strategy for achieving a high level of heterodimer purity. And robust operation range of anion exchange chromatography steps for homodimer removal was also developed by leveraging the design of experiments.

Has pilot zones policy for green finance reform and innovations improved the level of green financial development and environmental quality?

This study uses the green finance reform and innovation pilot zone policy approved by the State Council in 2017 as a quasi-natural experiment to explore whether the implementation of the policy has improved the level of green finance development and environmental quality in Chinese cities at the prefecture level and above. The results show that the green financial reform and innovation pilot zone policy can significantly improve the level of regional green financial development and environmental quality, and the results are robust. Further heterogeneity analysis finds that the green financial reform and innovation pilot zone policy have heterogeneous effects on the level of green financial development and environmental quality in different regions, sizes, environmental regulation intensity, financial development levels, and cities of different administrative levels. Based on this conclusion, suggestions are made that the scope should be further expanded and green finance policies should be formulated differently.

China's green data center development:Policies and carbon reduction technology path.

Data center is a very important infrastructure to support the development of information technology, and its development and increment are very remarkable. However, with the rapid and large-scale development of data centers, the problem of energy consumption turns to be also very prominent. Under the background of global carbon peak and carbon neutrality, developing green and low-carbon data centers has become an inevitable trend. This paper reviews and analyzes the policies and their roles in promoting China's green development of data centers in the past 10 years, summarizes the current situation of the implementation of green data center projects in China and gives the changes of PUE limits of data centers under the policy constraints. Application of green technologies is an important measure for energy-saving and low-carbon development of data centers, so encouraging innovation and application of green technologies in data center is also a priority task in relevant policies. This paper points out the green and low-carbon technology system of data centers, further summarizes energy-saving and carbon-reducing technologies in IT equipment, cooling system, power supply and distribution system, lighting, intelligent operation and maintenance, and provides an outlook on the future green development of data centers.

Fabrication of superhydrophilic porous carbon materials through a porogen-free method: Surface and structure modification promoting the two-electron oxygen reduction activity.

HYPOTHESIS: Electrochemical manufacture of H2O2 through the two-electron oxygen reduction reaction (2e- ORR), providing prospects of the distributed production of H2O2 in remote regions, is considered a promising alternative to the energy-intensive anthraquinone oxidation process. EXPERIMENTS: In this study, one glucose-derived oxygen-enriched porous carbon material (labeled as HGC500) is developed through a porogen-free strategy integrating structural and active site modification. FINDINGS: The superhydrophilic surface and porous structure together promote the mass transfer of reactants and accessibility of active sites in the aqueous reaction, while the abundant CO species (e.g., aldehyde groups) are taken for the main active site to facilitate the 2e- ORR catalytic process. Benefiting from the above merits, the obtained HGC500 possesses superior performance with a selectivity of 92 % and mass activity of 43.6 A gcat-1 at 0.65 V (vs. RHE). Besides, the HGC500 can operate steadily for 12 h with the accumulation of H2O2 reaching up to 4090±71 ppm and a Faradic efficiency of 95 %. The H2O2 generated from the electrocatalytic process in 3 h can degrade a variety of organic pollutants (10 ppm) in 4-20 min, displaying the potential in practical applications.

State-of-the-Art Advancements in Photocatalytic Hydrogenation: Reaction Mechanism and Recent Progress in Metal-Organic Framework (MOF)-Based Catalysts.

Photocatalytic hydrogenation provides an effective alternative way for the synthesis of industrial chemicals to meet the economic and environment expectations. Especially, over the past few years, metal-organic frameworks (MOFs), featured with tunable structure, porosity, and crystallinity, have been significantly developed as many high-performance catalysts in the field of photocatalysis. In this review, the background and development of photocatalytic hydrogenation are systemically summarized. In particular, the comparison between photocatalysis and thermal catalysis, and the fundamental understanding of photohydrogenation, including reaction pathways, reducing species, regulation of selectivity, and critical parameters of light, are proposed. Moreover, this review highlights the advantages of MOFs-based photocatalysts in the area of photohydrogenation. Typical effective strategies for modifying MOFs-based composites to produce their advantages are concluded. The recent progress in the application of various types of MOFs-based photocatalysts for photohydrogenation of unsaturated organic chemicals and carbon dioxide (CO2 ) is summarized and discussed in detail. Finally, a brief conclusion and personal perspective on current challenges and future developments of photocatalytic hydrogenation processes and MOFs-based photocatalysts are also highlighted.

Methane Dry Reforming by Ni-Cu Nanoalloys Anchored on Periclase-Phase MgAlOx Nanosheets for Enhanced Syngas Production.

Stable and efficient syngas production via methane dry reforming is highly desirable as it utilizes two greenhouse gases simultaneously. In this work, active Ni-Cu nanoalloys stably anchored on periclase-phase MgAlOx nanosheets were successfully synthesized by a hydrothermal method. These highly dispersed small Ni-Cu alloys strongly interacted with the periclase-phase MgAlOx nanosheets, on which abundant base sites were accessible. On the optimal catalyst (6Ni6CuMgAl-S), methane and carbon dioxide conversion always reached 85 and 90% at 700 °C under a gas hour speed velocity of 40,000 mL/gcat h for more than 70 h. The hydrogen production rate was maintained at 1.8 mmol/min, and the ratio of H2/CO was kept at approximately 0.96 under a CH4 and CO2 flow rate of 25 mL/min. Coke deposition and Ni sintering were effectively suppressed by the formation of a Ni-Cu alloy, the laminar structure, and the periclase phase of the MgAlOx support. Moreover, the alloy nanoparticles were reconstructed into a segregated Ni-Cu alloy structure in response to the reaction environment, and this structure was more stable and still active. Density functional theory calculations showed that carbon adsorption was inhibited on the segregated Ni-Cu alloy. Furthermore, the experimental thermogravimetric and O2-TPO results confirmed the significant decrease in carbon deposition on the Ni-Cu alloy catalysts.

Validation of ICON-MIGHTI Thermospheric Wind Observations: 2. Green-Line Comparisons to Specular Meteor Radars.

We compare coincident thermospheric neutral wind observations made by the Michelson Interferometer for Global High-Resolution Thermospheric Imaging (MIGHTI) on the Ionospheric Connection Explorer (ICON) spacecraft, and four ground-based specular meteor radars (SMRs). Using the green-line MIGHTI channel, we analyze 1158 coincidences between Dec 2019 and May 2020 in the altitude range from 94 to 104 km where the observations overlap. We find that the two datasets are strongly correlated (r = 0.82) with a small mean difference (4.5 m/s). Although this agreement is good, an analysis of known error sources (e.g., shot noise, calibration errors, and analysis assumptions) can only account for about a quarter of the disagreement variance. The unexplained variance is 27.8% of the total signal variance and could be caused by unknown errors. However, based on an analysis of the spatial and caused by temporal variability of the wind on scales ≲70 min. The observed magnitudes agree well during temporal averaging of the two measurement modalities, we suggest that some of the disagreement is likely the night, but during the day, MIGHTI observes 16%-25% faster winds than the SMRs. This remains unresolved but is similar in certain ways to previous SMR-satellite comparisons.

Subsurface-Regulated PtGa Nanoparticles Confined in Silicalite-1 for Propane Dehydrogenation.

Propane dehydrogenation (PDH) is one of the most promising techniques to produce propylene. Industrial Pt-based catalysts often suffer from short-time stability under high temperature due to serious sintering and coke deposition via undesired side reactions. Detailed reaction mechanism on the surface of Pt-based nanoparticle has been well studied, while the subsurface effect remains mostly unstudied. Herein, supported PtGa nanoparticles with different surface and subsurface composition was evidenced by extended X-ray absorption fine structure (EAXFS) spectra and energy dispersive X-ray spectroscopy (EDS). Theoretical simulation demonstrated subsurface regulation would increase the electron density of surface Pt and thus weaken propylene adsorption. Propylene selectivity on the PtGa-subsurface nanoparticles was up to 98% at 600 °C while that on the Pt-subsurface nanoparticles was only 95%. Furthermore, rational designed PtGa alloy nanoparticles were encapsulated in MFI zeolite to inhibit sintering and coke deposition for enhanced catalytic stability.

Impact of China's water pollution on agricultural economic growth: an empirical analysis based on a dynamic spatial panel lag model.

The average annual growth rate of China's waste emissions from 2007 to 2017 was 2.3%. The main pollutants in the wastewater are chemical oxygen demand, ammonia nitrogen, total ammonia, total phosphorus, and so on which pollute groundwater and destroy ecosystems. Poor water quality reduces the edible value of agricultural products and has an impact on human health. Based on the panel data of 31 provinces in China from 2007 to 2017, this paper uses a dynamic spatial panel lag model to study the impact of China's water pollution on agricultural economic growth. The results show that the impact of China's water pollution on agricultural economic growth is significant. If the intensity of wastewater discharge is taken as an input factor in the process of agricultural production, the growth of agricultural economy tends to decline with the increase of water pollution. In the effect analysis, the short-term and long-term effects are significant. The absolute value of the long-term total effect is far greater than the short-term total effect, indicating that the inhibitory effect of water pollution on agricultural economic growth is more obvious. The cumulative effect of water pollution on agricultural economic growth continues to expand, resulting in more and more economic losses. The central and local governments should take various measures to reduce water pollution, guide the green development of agriculture, and increase farmers' income to realize the rural revitalization plan.

Does environmental regulation reduce China's haze pollution? An empirical analysis based on panel quantile regression.

Haze pollution in China is very serious and has become the source of mortality, affecting the health and lives of residents. The Chinese government adopts different policy measures to reduce haze pollution. The impact of different types of environmental regulations on haze pollution has become a hot topic for academics and government departments. Based on panel data from 2005-2017, this paper studies the effect of different types of environmental regulations on haze pollution in 30 provinces of China using a panel quantile model. The results show that when haze pollution changes from a low quantile to a high quantile, the marginal impact of command-and-control environmental regulation on haze pollution changes from 0.122 to -0.332. Command-and-control environmental regulation can reduce haze pollution, but its impact is not significant. The main reason for this finding is that environmental law enforcement is not strict. The marginal impact of economically restrained environmental regulation on haze pollution changes from -14.389 to 49.939. Economically restrained environmental regulation can reduce haze pollution in low quantiles, but not in high quantiles. The collection of sewage charges fees is far less than the total profit, which has no deterrent effect on enterprises. The marginal impact of public participation in environmental regulation on haze pollution changes from 0.154 to -0.002. Public participation in environmental regulation cannot reduce haze pollution in low quantiles, but can in high quantiles; however its impact becomes insignificant. This study reveals the quantile-based discrepancy in the effect of environmental regulation on haze pollution, and offers a new perspective for research on the effects of environmental regulation.

Chiral Bicyclo[2.2.2]octane-Fused CpRh Complexes: Synthesis and Potential Use in Asymmetric C-H Activation.

A new class of chiral cyclopentadienyl rhodium(I) complexes (CpRhI ) bearing C2 -symmetric chiral bridged-ring-fused Cp ligands was prepared. The complexes were successfully applied to the asymmetric C-H activation reaction of N-methoxybenzamides with quinones, affording a series of chiral hydrophenanthridinones in up to 82 % yield with up to 99 % ee. Interestingly, structure analysis reveals that the side wall of the optimal chiral CpRhI catalyst is vertically more extended, horizontally less extended, and closer to the metal center in comparison with the classic binaphthyl and spirobiindanyl CpRhI complexes, and may thus account for its superior catalytic performance.

China's energy consumption and green economy efficiency: an empirical research based on the threshold effect.

Using the panel data of China's provinces from 2005 to 2016, the paper adopts the ultra-efficiency model to measure the green economy efficiency of each province. Then, the paper used the panel threshold model to study the impact of science and technological input on the green economy efficiency with the energy consumption intensity as a threshold variable. The results show that the green economy efficiency in China's provinces is low and is in a downward trend. When the energy consumption intensity is the threshold variable, the single-threshold effect is significant. When the energy consumption intensity is lower than the threshold value, the impact of science and technological input on green economic efficiency is not significant, and the energy consumption intensity has a significant impact on green economic efficiency with science and technological input and energy consumption intensity as the core explanatory variables and with energy consumption intensity as the threshold variable. When the energy consumption intensity crosses the threshold value, the impact of science and technological input and energy consumption intensity on green economic efficiency becomes significant. According to the above empirical results, this paper proposes corresponding countermeasures and suggestions.

Metal-Free Chemoselective Hydrogenation of Nitroarenes by N-Doped Carbon Nanotubes via In Situ Polymerization of Pyrrole.

Chemoselective hydrogenation of nitroarenes to anilines is of great importance for the manufacture of pharmaceuticals, fine chemicals, and dyes. In this study, a series of metal-free N-doped carbon nanotubes (NCNTs) have been prepared by the carbonization of in situ polymerized pyrrole on CNTs. The concentration of pyrrole, pyrolysis temperature, and the outside diameter of CNTs were investigated to improve the catalytic performance. As characterized by Raman and X-ray photoelectron spectroscopy (XPS), the optimal catalyst (NCNTs-800) possessed a unique structure doped with the same content of pyrrolic N and graphitic N. The activity and selectivity of NCNTs-800 have been evaluated for the selective hydrogenation of substituted nitroarenes. Highly selective hydrogenation of the nitro group of 12 different substrates has been achieved on NCNTs-800, even in the presence of a fragile iodo group. The hydrogenation reaction on N-doped CNTs from polypyrrole involved a mixture of different hydrogen species including nonpolar H radicals. In addition, stability and recyclability of NCNTs-800 have been tested.

Understanding deep dehydrogenation and cracking of n-butane on Ni(111) by a DFT study.

Steam reforming is a main industrial process for hydrogen production. In particular, with the carbon chain increasing to n-butane, a main component in liquefied petroleum gas (LPG) and shale oil gas, chemically different C-C bonds ((C-C)α,ß and (C-C)ß,ß') will be involved in cleavages. In addition, understanding the role of catalysis in these pathways is critical toward the advancement in technology, yet is largely lacking. As such, we have performed density functional theory (DFT) calculations to study the two possible C-C cleavage pathways of n-butane on Ni(111), i.e., the (C-C)α,ß cleavage from the n-butane deep dehydrogenation product of 1-butyne, and the (C-C)ß,ß' cleavage from 2-butyne. The results indicate that these two different pathways have distinct dehydrogenations to butyne, and that Ni is suitable for the deep dehydrogenation. The C-C cleavage in both pathways serves as the rate-determining step with a higher energy barrier than that for the preceding C-H bond cleavage. In addition, the 1-butyne pathway was found to be more favorable than that of 2-butyne in thermodynamics and kinetics. Our results provide insights into the alkane dehydrogenation and cracking of long-chain hydrocarbons on Ni-based catalysts.

Ruthenium(II)-Catalyzed Asymmetric Inert C-H Bond Activation Assisted by a Chiral Transient Directing Group.

A ruthenium(II)-catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. A series of 2,3-dihydrobenzofurans bearing chiral all-carbon quaternary stereocenters have been prepared in remarkably high yields (up to 98 %) and enantioselectivities (up to >99 % ee). By this methodology, a novel asymmetric total synthesis of CB2 receptor agonist MDA7 has been successfully developed.

Phytosphinganine Affects Plasmodesmata Permeability via Facilitating PDLP5-Stimulated Callose Accumulation in Arabidopsis.

Plant plasmodesmata (PDs) are specialized channels that enable communication between neighboring cells. The intercellular permeability of PDs, which affects plant development, defense, and responses to stimuli, must be tightly regulated. However, the lipid compositions of PD membrane and their impact on PD permeability remain elusive. Here, we report that the Arabidopsis sld1 sld2 double mutant, lacking sphingolipid long-chain base 8 desaturases 1 and 2, displayed decreased PD permeability due to a significant increase in callose accumulation. PD-located protein 5 (PDLP5) was significantly enriched in the leaf epidermal cells of sld1 sld2 and showed specific binding affinity to phytosphinganine (t18:0), suggesting that the enrichment of t18:0-based sphingolipids in sld1 sld2 PDs might facilitate the recruitment of PDLP5 proteins to PDs. The sld1 sld2 double mutant seedlings showed enhanced resistance to the fungal-wilt pathogen Verticillium dahlia and the bacterium Pseudomonas syringae pv. tomato DC3000, which could be fully rescued in sld1 sld2 pdlp5 triple mutant. Taken together, these results indicate that phytosphinganine might regulate PD functions and cell-to-cell communication by modifying the level of PDLP5 in PD membranes.