Subconjunctival Administration of an Adeno-Associated Virus Expressing Stanniocalcin-1 Provides Sustained Intraocular Pressure Reduction in Mice.

Purpose: To investigate subconjunctival administration of a single-stranded, adeno-associated virus, serotype 2, engineered to express stanniocalcin-1 with a FLAG tag (ssAAV2-STC-1-FLAG) as a novel sustained (IOP) lowering agent with a reduced ocular surface side effect profile. Design: In vivo preclinical investigation in mice. Subjects: C57BL/6J, DBA/2J, prostaglandin F (FP) receptor knockout mice. Methods: Normotensive C57BL/6J mice were treated with a subconjunctival injection of ssAAV2-STC-1-FLAG (2 µL; 6 × 109 viral genomes [VGs]) in 1 eye and the same volume and concentration of ssAAV2-green fluorescent protein (GFP) or the same volume of phosphate-buffered saline in the fellow eye. Ocular hypertensive DBA/2J mice were subconjunctivally injected with 6 × 109 VGs of ssAAV2-STC-1-FLAG or ssAAV2-GFP. Steroid-mediated ocular hypertension was induced in C57BL/6J mice with weekly injections of dexamethasone into the conjunctival fornix, and mice were then injected subconjunctivally with 6 × 109 VGs of ssAAV2-STC-1-FLAG or ssAAV2-GFP. Prostaglandin F receptor knockout mice were injected subconjunctivally with 6 × 109 VGs of ssAAV2-STC-1-FLAG or phosphate-buffered saline. An identical vector was constructed without the FLAG tag (ssAAV2-STC-1) and evaluated in normotensive C57BL/6J mice. Intraocular pressure was assessed using the Tonolab tonometer for all experiments. Tumor necrosis factor alpha (TNFα), a marker of ocular surface inflammation, was compared between subconjunctivally delivered ssAAV2-STC-1-FLAG and other treatments including daily topical latanoprost. Main Outcome Measures: Intraocular pressure assessment. Results: Subconjunctival delivery of ssAAV2-STC-1-FLAG significantly reduced IOP for 10 weeks post injection in normotensive mice. Maximal IOP reduction was seen at week 3 postinjection (17.4%; 17.1 ± 0.8 vs. 14.1 ± 0.8 mmHg, P < 0.001). After the IOP-lowering effect had waned, a second injection restored the ocular hypotensive effect. Subconjunctivally delivered ssAAV2-STC-1-FLAG lowered IOP in DBA/2J mice (16.9%; 17.8 ± 2.0 vs. 14.8 ± 0.9 mmHg, P < 0.001) and steroid-mediated ocular hypertensive mice (20.0%; 19.0 ± 0.6 vs. 15.2 ± 0.7 mmHg, P < 0.001) over the experimental period. This construct also reduced IOP to a similar extent in wild-type (15.9%) and FP receptor knockout (15.7%) mice compared with the fellow eye. A related construct also lowered IOP without the FLAG tag in a similar manner. Reduction in conjunctival TNFα was seen when comparing subconjunctivally delivered ssAAV2-STC-1-FLAG to daily topical latanoprost. Conclusions: Subconjunctival delivery of the STC-1 transgene with a vector system may represent a novel treatment strategy for sustained IOP reduction and improved ocular tolerability that also avoids the daily dosing requirements of currently available medications. Financial Disclosures: Proprietary or commercial disclosure may be found in the Footnotes and Disclosures at the end of this article.

Dynamic evaluation of China's atmospheric environmental pressure from 2008 to 2017: Trends and drivers.

Evaluating the pressure of atmospheric pollutant emissions on the atmospheric environment is crucial for effective pollution control and emission reduction policies. This study introduces a novel Atmospheric Environmental Pressure Index (AEPI) and employs a dynamic comprehensive method to evaluate China's Atmospheric Environmental Pressure (AEP) across 31 provinces from 2008 to 2017. The drivers of AEP were analyzed using a spatial panel data model, uncovering the integral role of pollution reduction policies, particularly the Air Pollution Prevention and Control Action Plan, which led to a 25% reduction in AEP during its enforcement. Our findings reveal significant spatial disparities in AEP, with higher levels in the Beijing-Tianjin-Hebei and Yangtze River Delta regions. The regression analysis identifies economic development, industrial structure, energy efficiency, environmental regulations, and urbanization as key influencing factors, though their impacts vary across different regions, suggesting the need for region-specific pollution control policies. Furthermore, the shift in the AEP gravity center from 2008 to 2017 indicated a southeastward movement, suggesting the necessity to focus air pollution control efforts on the southeast provinces. In conclusion, the AEPI developed in this study enables comparative analysis of AEP across different regions and facilitates the monitoring of long-term trends, which is valuable in guiding regional air pollution control in China.

Efficient electroreduction of carbon dioxide to formate enabled by bismuth nanosheets enriched dual VBi0 vacancy.

The electrocatalytic reduction of carbon dioxide (CO2ER) into formate presents a compelling solution for mitigating dependence on fossil energy and green utilization of CO2. Bismuth (Bi) has been gaining recognition as a promising catalyst material for the CO2ER to formate. The performance of Bi catalysts (named as Bi-V) can be significantly improved when they possess single metal atom vacancy. However, creating larger-sized metal atom vacancies within Bi catalysts remains a significant challenge. In this work, Bi nanosheets with dual VBi0 vacancy (Bi-DV) were synthesized utilizing in situ electrochemical transformation, using BiOBr nanosheets with triple vacancy associates (VBi″'VO··VBi″', VBi″' and VO·· denote the Bi3+ and O2- vacancy, respectively) as a template. The obtained Bi-DV achieved higher CO2ER activity than Bi-V, showing Faradaic efficiency for formate production of >92% from -0.9 to -1.2 VRHE in an H-type cell, and the partial current density of formate reached up to 755 mA/cm2 in a flow cell. The comprehensive characterizations coupled with density functional theory calculations demonstrate that the dual VBi0 vacancy on the surface of Bi-DV expedite the reaction kinetics toward CO2ER, by reducing the thermodynamic barrier of *OCHO intermediate formation. This research provides critical insights into the potential of large atom vacancies to enhance electrocatalysis performance.

Establish of air pollutants and greenhouse gases emission inventory and co-benefits of their reduction of transportation sector in Central China.

Recently, the transportation sector in China has gradually become the main source of urban air pollution and primary driver of carbon emissions growth. Considering air pollutants and greenhouse gases come from the same emission sources, it is necessary to establish an updated high-resolution emission inventory for the transportation sector in Central China, the most polluted region in China. The inventory includes on-road mobile, non-road mobile, oil storage and transportation, and covers 9 types of air pollutants and 3 types of greenhouse gases. Based on the Long-range Energy Alternatives Planning System (LEAP) model, the emissions of pollutants were predicted for the period from 2020 to 2035 in different scenarios. Results showed that in 2020, emissions of SO2, NOx, CO, PM10, PM2.5, VOCs, NH3, BC, OC, CO2, CH4, and N2O in Henan Province were 27.5, 503.2, 878.6, 20.1, 17.4, 222.1, 21.5, 9.4, 2.9, 92,077.9, 6.0, and 10.4 kilotons, respectively. Energy demand and pollutant emissions in Henan Province are simulated under four scenarios (Baseline Scenario (BS), Pollution Abatement Scenario (PA), Green Transportation Scenario (GT), and Reinforcing Low Carbon Scenario (RLC)). The collaborative emission reduction effect is most significant in the RLC scenario, followed by the GT scenario. By 2035, under the RLC scenario, energy consumption and emissions of SO2, NOx, CO, PM10, PM2.5, VOCs, NH3, CO2, CH4, and N2O are projected to decrease by 72.0%, 30.0%, 55.6%, 56.0%, 38.6%, 39.7%, 51.5%, 66.1%, 65.5%, 55.4%, and 52.8%, respectively. This study provides fundamental data support for subsequent numerical simulations.

Insight into the crystal facet-dependent Cr(VI) reduction: A comparative study of pyrite {100} and {111} facets.

The migration and transformation of hexavalent chromium (Cr(VI)) in the environment are regulated by pyrite (FeS2). However, variations in pyrite crystal facets influence the adsorption behavior and electron transfer between pyrite and Cr(VI), thereby impacting the Cr(VI) reduction performance. Herein, two naturally common facets of pyrite were synthesized hydrothermally to investigate the facet-dependent mechanisms of Cr(VI) reduction. The experimental results revealed that the {111} facet exhibited approximately 1.30-1.50 times higher efficiency in Cr(VI) reduction compared to the {100} facet. Surface analyses and electrochemical results indicated that {111} facet displayed a higher iron-sulfur oxidation level, which was affected by its superior electrochemical properties during the reaction with Cr(VI). Density functional theory (DFT) calculations demonstrated that the narrower band gap and lower work function on {111} facet were more favorable for the electron transfer between Fe(II) and Cr(VI). Furthermore, different adsorption configurations were observed on {100} and {111} surfaces due to the unique arrangements of Fe and S atoms. Specifically, O atoms in Cr2O72- directly bound with the S sites on {100} but the Fe sites on {111}. According to the density of states (DOS), the Fe site had better reactivity than the S site in the reaction, which appeared to be related to the fracture of S-S bonds. Additionally, the adsorption configuration of Cr2O72- on {111} surface showed a stronger adsorption energy and a more stable coordination mode, favoring subsequent Cr(VI) reduction process. These findings provide an in-depth analysis of facet-dependent mechanisms underlying Cr(VI) reduction behavior, offering new insights into studying environmental interactions between heavy metals and natural minerals.

Different behavior of food-related benzoic acids toward iron and copper.

Benzoic acids, which are commonly found in food, are also produced by human microbiota from other dietary phenolics. The aim was to investigate the interactions of 8 food-related benzoic acids with the physiological metals iron and copper under different (patho)physiologically relevant pH conditions in terms of chelation, reduction, impact on the metal-based Fenton chemistry, and copper-based hemolysis. Only 3,4-dihydroxybenzoic acid behaved as a protective substance under all conditions. It chelated iron, reduced both iron and copper, and protected against the iron and copper-based Fenton reaction. Conversely, 2,4,6-trihydroxybenzoic acid did not chelate iron and copper, reduced both metals, potentiated the Fenton reaction, and worsened copper-based hemolysis of rat red blood cells. The other tested compounds showed variable effects on the Fenton reaction. Interestingly, prooxidative benzoic acids mildly protected human erythrocytes against Cu-induced lysis. In conclusion, 3,4-dihydroxybenzoic acid seems to have a protective effect against copper and iron-based toxicity under different conditions.

Chemical reduction-induced defect-rich bismuth oxide-reduced graphene oxide anode for high-performance supercapacitors.

We prepare bismuth oxide-reduced graphene oxide (Bi2O3-rGO) composite anode using a one-step chemical precipitation/reduction method. Under a reducing atmosphere, oxygen atoms on the surface of Bi2O3 are gradually removed and neighboring oxygen atoms migrate to the surface, leaving oxygen vacancies. Defective Bi2O3 enhances the number of active sites, providing additional pseudocapacitive performance. The transition metal oxide-based Bi2O3 acts as an anode, providing capacitive performance that far exceeds that of conventional carbon materials. Moreover, the introduction of rGO forms a conductive network for Bi2O3, improving capacitive contribution and ion diffusion capabilities for the electrode. The Bi2O3-rGO-100 (GO added at 100 mg) exhibits a high specific capacitance of 1053F/g at 1 A/g, significantly higher than that of Bi2O3 (866F/g). The Bi2O3-rGO-100 anode and Ni3Co2-rGO cathode are assembled into a battery-type supercapacitor. The coin-cell device achieves an energy density of 88.2 Wh kg-1 at a power density of 850 W kg-1. The Ni3Co2-rGO//Bi2O3-rGO-100 pouch-cell device demonstrates an extremely low Rct of 0.77 Ω. At a power density of 850 W kg-1, the energy density reaches 118.5 Wh kg-1, and remains 67.4 Wh kg-1 at 8500 W kg-1.

La doped-Fe2(MoO4)3 with the synergistic effect between Fe2+/Fe3+ cycling and oxygen vacancies enhances the electrocatalytic synthesizing NH3.

The electrocatalytic nitrogen reduction reaction (NRR) is a crucial process in addressing energy shortages and environmental concerns by synthesizing the NH3. However, the difficulty of N2 activation and fewer NRR active sites limit the application of NRR. Therefore, the NRR performance can be improved by rapid electron transport paths to participate in multi-electron reactions and N2 activation. Doping with transition metal element is a viable strategy to provide electrons and electronic channels in the NRR. This study focuses on the synthesis of Fe2(MoO4)3 (FeMo) and x%La-doped FeMo (x = 3, 5, 7, and 10) using the hydrothermal method. La-doping creates electron transport channels Fe2+-O2--Fe3+ and oxygen vacancies, achieving an equal molar ratio of Fe2+/Fe3+. This strategy enables the super-exchange in Fe2+-O2--Fe3+, and then enhances electron transport speed for a rapid hydrogenation reaction. Therefore, the synergistic effect of Fe2+/Fe3+ cycling and oxygen vacancies improves the NRR performance. Notably, 5%La-FeMo demonstrates the superior NRR performance (NH3 yield rate: 29.6 µg h-1 mgcat-1, Faradaic efficiency: 5.8%) at -0.8 V (vs. RHE). This work analyzes the influence of the catalyst electronic environment on the NRR performance based on the effect on different valence states of ions on electron transport.

Heteropoly blue-modified ultrathin bismuth oxychloride nanosheets with oxygen vacancies for efficient photocatalytic nitrogen fixation in pure water.

Photocatalytic nitrogen reduction is a promising green technology for ammonia synthesis under mild conditions. However, the poor charge transfer efficiency and weak N2 adsorption/activation capability severely hamper the ammonia production efficiency. In this work, heteropoly blue (r-PW12) nanoparticles are loaded on the surface of ultrathin bismuth oxychloride nanosheets with oxygen vacancies (BiOCl-OVs) by electrostatic self-assembly method, and a series of xr-PW12/BiOCl-OVs heterojunction composites have been prepared. Acting as a robust support, ultrathin two-dimensional (2D) structure of BiOCl-OVs inhibits the aggregation of r-PW12 nanoparticles, enhancing the interfacial contact between r-PW12 and BiOCl. More importantly, the existence of oxygen vacancies (OVs) provides abundant active sites for efficient N2 adsorption and activation. In combination of the enhanced light absorption and promoted photogenerated carriers separation of xr-PW12/BiOCl-OVs heterojunction, under simulated solar light, the optimal 7r-PW12/BiOCl-OVs exhibits an excellent photocatalytic N2 fixation rate of 33.53 µmol g-1h-1 in pure water, without the need of sacrificial agents and co-catalysts. The reaction dynamics is also monitored by in situ FT-IR spectroscopy, and an associative distal pathway is identified. Our study demonstrates that construction of heteropoly blues-based heterojunction is a promising strategy for developing high-performance N2 reduction photocatalysts. It is anticipated that combining of different defects with heteropoly blues of different structures might provide more possibilities for designing highly efficient photocatalysis systems.

Janus structural TaON/Graphene-like carbon dual-supported Pt electrocatalyst enables efficient oxygen reduction reaction.

Developing carbon-supported Pt-based electrocatalysts with high activity and long-durability for the oxygen reduction reaction (ORR) is an enormous challenge for their commercial applications due to the corrosion of carbon supports in acid/alkaline solution at high potential. In this work, a Janus structural TaON/graphene-like carbon (GLC) was synthesized via an in-situ molecular selfassembly strategy, which was used as a dual-carrier for platinum (Pt). The as-obtained Pt/TaON/GLC presents high half-wave potential (0.94 V vs. RHE), excellent mass (1.48 A mgPt-1) and specific (1.75 mA cmPt-2) activities at 0.9 V, and superior long-term durability with a minimal loss (8.0 %) of mass activity after 10,000 cycles in alkaline solution, outperforming those of Pt/C and other catalysts. The structural characterizations and density functional theory (DFT) calculations indicate that the Pt/TaON/GLC catalyst exhibits the maximum synergies, including enhanced interfacial electron density, improved charge transfer, enhanced O2 adsorption, andsuperimposed OO cleavage. This work shows a potential strategy for preparing the high-active and long-durable Pt-based electrocatalyst by synergism-promoted interface engineering.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction.

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.

Boosted electrocatalytic activity and durability of CuFe/NC by modulating the interfacial composition and electronic structure for efficient oxygen reduction reaction.

Oxygen reduction reaction (ORR) serves as the foundation for various electrochemical energy storage devices. Fe/NC catalysts are expected to replace commercial Pt/C as oxygen electrode catalysts based on the structural tunability at the atomic level, abundant iron ore reserves and excellent activity. Nevertheless, the lack of durability and low active site density impede its advancement. In this work, a durable catalyst, CuFe/NC, for ORR was prepared by modulating the interfacial composition and electronic structure. The introduction of Cu nanoclusters partially eliminates the Fenton effect from Fe and optimizes the electron structure of FeNx, thereby effectively enhancing the long-term durability and activity. The prepared CuFe/NC exhibits a half-wave potential (E1/2) of 0.90 V and superior stability with a decrease in E1/2 of only 20 mV after 10,000 cycles. The assembled alkaline Zinc-Air batteries (ZABs) with CuFe/NC exhibit an open-circuit potential of 1.458 V. At a current density of 5 mA cm-2, the batteries are capable of operation for 600 h with a stable polarization. This CuFe/NC may promote the practical application of novel and renewable electrochemical energy storage devices.

MOF-on-MOF-derived FeCo@NC OER&ORR bifunctional electrocatalysts for zinc-air batteries.

Zinc-air batteries, as one of the emerging areas of interest in the quest for sustainable energy solutions, are hampered by the intrinsically sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and still suffer from the issues of low energy density. Herein, we report a MOF-on-MOF-derived electrocatalyst, FeCo@NC-II, designed to efficiently catalyze both ORR (Ehalf = 0.907 V) and OER (Ej=10 = 1.551 V) within alkaline environments, surpassing esteemed noble metal benchmarks (Pt/C and RuO2). Systematically characterizations and density functional theory (DFT) calculations reveal that the synergistic effect of iron and cobalt bimetallic and the optimized distribution of nitrogen configuration improved the charge distribution of the catalysts, which in turn optimized the adsorption / desorption of oxygenated intermediates accelerating the reaction kinetics. While the unique leaf-like core-shell morphology and excellent pore structure of the FeCo@NC-II catalyst caused the improvement of mass transfer efficiency, electrical conductivity and stability. The core and shell of the precursor constructed through the MOF-on-MOF strategy achieved the effect of 1 + 1 > 2 in mutual cooperation. Further application to zinc-air batteries (ZABs) yielded remarkable power density (212.4 mW/cm2), long cycle (more than 150 h) stability and superior energy density (∼1060 Wh/kg Zn). This work provides a methodology and an idea for the design, synthesis and optimization of advanced bifunctional electrocatalysts.

The synergistic effect of Cl doping and Bi coupling to promote the carrier separation of BiOBr for efficient photocatalytic nitrogen reduction.

Photocatalytic nitrogen reduction reaction (NRR) is a sustainable process for ammonia synthesis under mild conditions. However, photocatalytic NRR activity and are generally limited by inefficient carrier separation and transfer. Therefore, parallel engineering of bulk phase doping and surface coupling is critical to achieving the goal of efficient NRR. In this study, Cl doped BiOBr nanosheet assemblies (BiOBr/Cl) were constructed in delicately designed deep eutectic solvents (DESs), combined with ionothermal methods at low temperatures and Bi3+ exsolution reduction strategy at high temperatures. The unique liquid state and reducibility of DESs induce the reduction of Bi3+ and the in situ coupling of Bi quantum dots at the surface of BiOBr/Cl nanosheets along with the construction of Bi-BiOBr/Cl nanosheet assemblies. The experimental results show that Cl doping could reduce the exciton dissociation energy and promote its dissociation to free carriers. Bi quantum dots could form tightly coupled Schottky junction with BiOBr/Cl enabling the efficient and unidirectional transmission of photogenerated electrons from BiOBr/Cl to metal Bi. The formed electron deficient region at Schottky interface promotes the adsorption and activation of N2. The hierarchical structure of Bi-BiOBr/Cl nanosheet assembly benefits to providing more N2 adsorption active sites. The DFT calculation shows that the accumulation of high concentration of active hydrogen in Bi-BiOBr/Cl leads to a significant decrease of energy barrier of the first step hydrogenation of N2. Bi-BiOBr/Clis more inclined to adsorb nitrogen for NRR in comparison with H* for hydrogen production. The synergistic effect of Cl doping and Bi coupling result in a high NRR activity of Bi-BiOBr/Cl photocatalyst of 6.67 mmol·g-1·h-1, which was 11.3 times higher than that of initial BiOBr. This study provides a promising strategy for designing highly active NRR photocatalysts with high efficiency carrier dissociation and transport.

Robust construction of CeNi quantum dots/Ni-MOL nanosheets for superior photocatalytic CO2 reduction.

Since the intensification of global environmental pollution and energy shortages, photocatalytic CO2 reduction reaction (CO2RR) has emerged as a promising strategy to convert solar energy into clean chemical energy. Herein, we construct a robust and efficient heterojunction construction photocatalyst for CO2RR, composed of the highly reactive CeNi quantum dots (CeNi QDs) and nickel metal-organic layer (Ni-MOL) ultrathin nanosheets. This design facilitates the rapid separation of photogenerated charge carriers, as confirmed by X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL) and other characterizations. Mechanistic studies with in situ diffuse reflectance Fourier transform infrared spectroscopy (in situ DRIFTS) and the d-band center calculation indicate that the propensity of photocatalyst for CO2 absorption and CO desorption, leading to high performance and selectivity. The optimized loading amount of CeNi quantum dots and modified structure result in a CO yield of 30.53 mmol·g-1 within 6 h under irradiation. This work not only paves a new and convenient way for developing high-activity quantum dot materials for CO2RR but also exploits novel avenues to fabricate more heterojunction composites for solar energy conversion.

Preparation of cathode catalysts for efficient direct lignin fuel cells by nitrogen doping reduction of oxidized graphene with phthalocyanine iron and Kraft lignin.

Direct lignin fuel cells (DLFC) are one of the important forms of high value-added utilization of lignin. In this study, lignin was studied not only as a fuel but also as a catalyst. Specifically, Kraft lignin was modified with ZnCl2, KOH and THF (Tetrahydrofuran) respectively, and added to the catalyst after activation. The results of scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive spectrometer (EDS), Brunauer - Emmett - Teller (BET), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FT-IR) and Raman spectra shown that AL/FePc-NrGO (activated lignin/iron phthalocyanine/nitrogen-doped reduction of graphene oxide) three-dimensional composite catalyst has been synthesized. The results showed that KOH-activated Kraft lignin had the best performance as an oxygen reduction reaction (ORR) catalyst, with a half-wave potential (E1/2) of 0.73 V and a limiting diffusion current density of 4.3 mA cm-1. The THF-modified catalyst showed similar stability and methanol resistance to 20 % Pt/C at ORR. The ORR catalyst applied to the DLFC has the best electrical performance with an open circuit voltage (OCV) was 0.53 V and the maximum power density it could reach 95.29 mW m-2 when the catalyst was modified with THF. It is encouraging that the AL/FePc-NrGO catalyst has better-generated electricity performance than 20 % Pt/C. This work has provided a new idea for developing non-noble metal catalysts and studying direct biomass liquid fuel cells.

Surface crystallized supramolecular to achieve highly dispersed ultrafine nano-palladium in-situ deposition to promote thermal/electrocatalytic reduction.

To promote the greening and economization of industrial production, the development of advanced catalyst manufacturing technology with high activity and low cost is an indispensable part. In this study, nitrogen-doped hollow carbon spheres (NHCSs) were used as anchors to construct a supramolecular coating formed by the self-assembly of boron clusters and ß-cyclodextrin by surface crystallization strategy, with the help of the weak reducing agent characteristics of boron clusters, highly dispersed ultra-small nano-palladium particles were in-situ embedded on the surface of NHCSs. The deoxygenation hydrogenation of nitroaromatics and the reduction of nitrate to ammonia were used as the representatives of thermal catalytic reduction and electrocatalytic reduction respectively. The excellent properties of the constructed Pd/NHCSs were proved by the probe reaction. In the catalytic hydrogenation of nitroaromatics to aminoaromatics, the reaction kinetic rate and activation energy are at the leading level. At the same time, the constructed Pd/NHCSs can also electrocatalytically reduce nitrate to high value-added ammonia with high activity and selectivity, and the behavior of Pd/NHCSs high selectivity driving nitrate conversion was revealed by density functional theory and in situ attenuated total reflection Fourier transform infrared (ATRFTIR) technique. These results all reflect the feasibility and superiority of in-situ anchoring ultra-small nano-metals as catalysts by surface crystallization to build a supramolecular cladding with reducing properties, which is an effective way to construct high-activity and low-cost advanced catalysts.

Modification of metals and ligands in two-dimensional conjugated metal-organic frameworks for CO2 electroreduction: A combined density functional theory and machine learning study.

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technology to establish an artificial carbon cycle. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with high electrical conductivity have great potential as catalysts. Herein, we designed a range of 2D c-MOFs with different transition metal atoms and organic ligands, TMNxO4-x-HDQ (TM = Cr∼Cu, Mo, Ru∼Ag, W∼Au; x  = 0, 2, 4; HDQ = hexadipyrazinoquinoxaline), and systematically studied their catalytic performance using density functional theory (DFT). Calculation results indicated that all of TMNxO4-x-HDQ structures possess good thermodynamic and electrochemical stability. Notably, among the examined 37 MOFs, 6 catalysts outperformed the Cu(211) surface in terms of catalytic activity and product selectivity. Specifically, NiN4-HDQ emerged as an exceptional electrocatalyst for CO production in CO2RR, yielding a remarkable low limiting potential (UL) of -0.04 V. CuN4-HDQ, NiN2O2-HDQ, and PtN2O2-HDQ also exhibited high activity for HCOOH production, with UL values of -0.27, -0.29, and -0.27 V, respectively, while MnN4-HDQ, and NiO4-HDQ mainly produced CH4 with UL values of -0.58 and -0.24 V, respectively. Furthermore, these 6 catalysts efficiently suppressed the competitive hydrogen evolution reaction. Machine learning (ML) analysis revealed that the key intrinsic factors influencing CO2RR performance of these 2D c-MOFs include electron affinity (EA), electronegativity (χ), the first ionization energy (Ie), p-band center of the coordinated N/O atom (εp), the radius of metal atom (r), and d-band center (εd). Our findings may provide valuable insights for the exploration of highly active and selective CO2RR electrocatalysts.

Multiplicative rGO/Cu-BDC MOF for 4-nitrophenol reduction and supercapacitor applications.

Two-dimensional nanosheets, with their distinct characteristics, are widely used in various applications such as water splitting, supercapacitors, catalysis etc. In this research, we produced Cu-BDC MOF nanosheets by using Cu2O nanotubes for metal ions and H2BDC as the organic linker. We combined these Cu-BDC MOF nanosheets with reduced graphene oxide (rGO) to form a nanocomposite. The collaboration between Cu-BDC MOF and rGO boosts both the catalytic reduction of 4-nitrophenol and the electrochemical capabilities. The conversion of 4-nitrophenol to 4-aminophenol is achieved using sodium borohydride as both a reducing agent and a catalyst. The study explores the impact of different concentrations of 4-nitrophenol and sodium borohydride on catalytic efficiency. The increase in sodium borohydride concentration enhances catalytic efficiency by providing more BH4- ions and electrons for the reduction process. The catalytic reduction process adheres to the Langmuir-Hinshelwood mechanism with apparent pseudo-first-order kinetics. Specifically, Cu-BDC MOF and rGO/Cu-BDC MOF exhibit specific capacities of 468.4 mA h/g and 656.4 mA h/g at a current density of 2 A/g, respectively, while also enhancing the operating voltage window. Therefore, electrodes based on rGO/Cu-BDC MOF nanosheets present a novel approach for environmental remediation and energy storage applications across various fields.

Engineering ZnIn2S4 with efficient charge separation and utilization for synergistic accelerate dual-function photocatalysis.

Combining photocatalytic reduction with organic synthetic oxidation in the same photocatalytic redox system can effectively utilize photoexcited electrons and holes from solar to chemical energy. Here, we stabilized 0D Au clusters on the substrate surface of Zn vacancies modified 2D ZnIn2S4 (ZIS-V) nanosheets by chemically bonding Au-S interaction, forming surfactant functionalized Au/ZIS-V photocatalyst, which can not only synergistic accelerate the selective oxidation of phenylcarbinol to value-added products coupled with clean energy hydrogen production but also further drive photocatalytic CO2-to-CO conversion. An internal electric field of Au/ZIS-V ohmic junction and Zn vacancies synchronously promote the photoexcited charge carrier separation and transfer to optimized active sites for redox reactions. Compared with CO2 reduction in water and the pristine ZnIn2S4, the reaction thermodynamics and kinetics of CO2 reduction over the Au/ZIS-V were simultaneously improved about 11.09 and 45.51 times, respectively. Moreover, the photocatalytic redox mechanisms were also profoundly studied by 13CO2 isotope tracing tests, in situ electron paramagnetic resonance (in situ EPR), in situ X-ray photoelectron spectroscopy (in situ XPS), in situ diffuse reflection infrared Fourier transform spectroscopy (in situ DRIFTS) and density functional theory (DFT) characterizations, etc. These results demonstrate the advantages of vacancies coupled with metal clusters in the synergetic enhancement of photocatalytic redox performance and have great potential applications in a wide range of environments and energy.