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This work introduces a new strategy of a single-atom nest catalyst, whereby several single atoms are positioned closely, aiming to achieve the dual benefits of high atom-utilization efficiency while avoiding the steric hindrance in the coupling reaction. As a proof of concept, Pt single-atom nests, where the adjacent Pt single atoms are approximately 4 Å apart, are precisely engineered on the TiO2 photocatalyst for photocatalytic non-oxidative coupling of methane. The Pt single-atom nest photocatalyst demonstrates remarkable activity, achieving a C2H6 yield and turnover frequency of 251.6 µmol gcat-1 h-1 and 20 h-1, respectively, representing a 3.2-fold improvement compared to the Pt single-atom photocatalyst. Density functional theory calculations reveal that the Pt single-atom nest can significantly decrease the energy barrier for the activation of both CH4 molecules in the coupling process.
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Constructing strong interfacial electric fields to enhance the surface charge transport kinetics is an effective strategy for promoting CO2 conversion. Herein, we present the fabrication of CdS-Bi2MoO6 Z-scheme heterojunctions with a robust internal electric field (IEF) using an in situ growth technique, establishing chemical bonding between the components. The IEF at the interface can offer an impetus for the segregation and transportation of photogenerated carriers, while the Cd-O chemical bonding mode acts as a rapid conduit for these carriers, thereby reducing the charge transfer distance. As a result, the Z-scheme charge transfer is accelerated due to the synergistic influence of these two factors. Therefore, the optimized CdS/Bi2MoO6 Z-scheme heterojunction possesses significantly enhanced dynamic carrier mobility, thus promoting the conversion of CO2 to CO without the need for additional co-catalysts or sacrificial agents. This optimization yields a remarkable CO selectivity of up to 97%. Meanwhile, the expedited Z-scheme charge transfer mechanism is validated through X-ray photoelectron spectroscopy, Kelvin probe force microscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy.
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The electrocatalytic conversion of inert CO2 to value-added chemical fuels powered by renewable energy is one of the benchmark approaches to address excessive carbon emissions and achieve carbon-neutral energy restructuring. However, the adsorption/activation of supersymmetric CO2 is facing insurmountable challenges that constrain its industrial-scale applications. Here, this theory-guided study confronts these challenges by leveraging the synergies of bimetallic sites and defect engineering, where pyrochlore-type semiconductor A2B2O7 is employed as research platform and the conversion of CO2-to-HCOOH as the model reaction. Specifically, defect engineering intensified greatly the chemisorption-induced CO2 polarization via the bimetallic coordination, thermodynamically beneficial to the HCOOH production via the *HCO2 intermediate. The optimal V-BSO-430 electrocatalyst with abundant surface oxygen vacancies achieved a superior HCOOH yield of 116.7 mmol h-1 cm-2 at -1.2 VRHE, rivalling the incumbent similar reaction systems. Furthermore, the unique catalytic unit featured with a Bi1-Sn-Bi2 triangular structure, which is reconstructed by defect engineering, and altered the pathway of CO2 adsorption and activation to allow the preferential affinity of the suspended O atom in *HCO2 to H. As a result, V-BSO-430 gave an impressive FEHCOOH of 93% at -1.0 VRHE. This study held promises for inspiring the exploration of bimetallic materials from the massive semiconductor database.
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Halogenated methane serves as a universal platform molecule for building high-value chemicals. Utilizing sodium chloride solution for photocatalytic methane chlorination presents an environmentally friendly method for methane conversion. However, competing reactions in gas-solid-liquid systems leads to low efficiency and selectivity in photocatalytic methane chlorination. Here, an in situ method is employed to fabricate a hydrophobic layer of TaOx species on the surface of NaTaO3. Through in-situ XPS and XANES spectra analysis, it is determined that TaOx is a coordination unsaturated species. The TaOx species transforms the surface properties from the inherent hydrophilicity of NaTaO3 to the hydrophobicity of TaOx/NaTaO3, which enhances the accessibility of CH4 for adsorption and activation, and thus promotes the methane chlorination reaction within the gas-liquid-solid three-phase system. The optimized TaOx/NaTaO3 photocatalyst has a good durability for multiple cycles of methane chlorination reactions, yielding CH3Cl at a rate of 233 µmol g-1 h-1 with a selectivity of 83%. In contrast, pure NaTaO3 exhibits almost no activity toward CH3Cl formation, instead catalyzing the over-oxidation of CH4 into CO2. Notably, the activity of the optimized TaOx/NaTaO3 photocatalyst surpasses that of reported noble metal photocatalysts. This research offers an effective strategy for enhancing the selectivity of photocatalytic methane chlorination using inorganic chlorine ions.
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Adsorption and activation of C-H bonds by photocatalysts are crucial for the efficient conversion of C-H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C-H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi2WO6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C-H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C-H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.
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Heavy metal pollution in urban river sediments is an important threat to river ecosystem health. To explore the temporal and spatial distribution characteristics of heavy metals in river sediments of Kaifeng City, the surface sediments of rivers were sampled in 2015 and 2021, respectively, and the contents of Cd, Cr, Cu, Ni, Pb, and Zn in sediments at different periods were compared. The heavy metal pollution in the two periods was evaluated using the indices of geo-accumulation, bio-toxicity risk assessment, and potential ecological risk. The results showed that the content of heavy metals in river sediments of Kaifeng City in 2021 were decreased significantly compared with that in 2015. Cd, Cr, Cu, Ni, Pb, and Zn decreased by 94.42%, 18.4%, 85.7%, 45.19%, 75.61%, and 92.28%, respectively. The heavy metal content in the Huafei River and Huiji River was higher than that in other rivers in both periods. Correlation and principal component analyses showed that the heavy metal pollution sources of river sediments in Kaifeng City were highly similar, and human activities such as industrial layout, road traffic, and land use were the main pollution sources. However, the results showed that the main pollutants were different between the two sampling times. In 2015, Cd, Cr, Pb, and Zn were the main pollutants, and in 2021, Cd, Cu, Pb, and Zn were the main pollutants. The results of the geo-accumulation, bio-toxicity risk assessment, and potential ecological risk indices showed that the temporal and spatial differences in heavy metal pollution in river sediments in Kaifeng City were large. However, the heavy metal pollution of the Huiji River and Huafei River was still serious, with contents in the medium and high pollution levels, especially to Cd. The heavy metal treatment of rivers in Kaifeng City has a long way to go, and it is particularly necessary to strengthen the engineering treatment for key river sections and effectively monitor key pollution elements.
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The keto-switched photocatalysis of covalent organic frameworks (COFs) for efficient H2 evolution was reported for the first time by engineering, at a molecular level, the local structure and component of the skeletal building blocks. A series of imine-linked BT-COFs were synthesized by the Schiff-base reaction of 1, 3, 5-benzenetrialdehyde with diamines to demonstrate the structural reconstruction of enol to keto configurations by alkaline catalysis. The keto groups of the skeletal building blocks served as active injectors, where hot π-electrons were provided to Pt nanoparticles (NPs) across a polyvinylpyrrolidone (PVP) insulting layer. The characterization results, together with density functional theory calculations, indicated clearly that the formation of keto-injectors not only made the conduction band level more negative, but also led to an inhomogeneous charge distribution in the donor-acceptor molecular building blocks to form a strong intramolecular built-in electric field. As a result, visible-light photocatalysis of TP-COFs-1 with one keto group in the skeletal building blocks was successfully enabled and achieved an impressive H2 evolution rate as high as 0.96â mmol g-1 h-1 . Also, the photocatalytic H2 evolution rates of the reconstructed BT-COFs-2 and -3 with two and three keto-injectors were significantly enhanced by alkaline post-treatment.
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A series of novel surface Ru-H bipyridine complexes-grafted TiO2 nanohybrids were for the first time prepared by a combined procedure of surface organometallic chemistry with post-synthetic ligand exchange for photocatalytic conversion of CO2 to CH4 with H2 as electron and proton donors under visible light irradiation. The selectivity toward CH4 increased to 93.4% by the ligand exchange of 4,4'-dimethyl-2,2'-bipyridine (4,4'-bpy) with the surface cyclopentadienyl (Cp)-RuH complex and the CO2 methanation activity was enhanced by 4.4-fold. An impressive rate of 241.2 µL·g-1·h-1 for CH4 production was achieved over the optimal photocatalyst. The femtosecond transient IR absorption results demonstrated that the hot electrons were fast injected in 0.9 ps from the photoexcited surface 4,4'-bpy-RuH complex into the conduction band of TiO2 nanoparticles to form a charge-separated state with an average lifetime of ca. 50.0 ns responsible for the CO2 methanation. The spectral characterizations indicated clearly that the formation of CO2â¢- radicals by single electron reduction of CO2 molecules adsorbed on surface oxygen vacancies of TiO2 nanoparticles was the most critical step for the methanation. Such radical intermediates were inserted into the explored Ru-H bond to generate Ru-OOCH species and finally CH4 and H2O in the presence of H2.
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Treatment of recalcitrant landfill leachate (LFL) induces huge energy consumption and carbon emissions due to its complex composition. Although membrane distillation (MD) exhibits good potential in LFL treatment with waste heat utilization, membrane fouling and ammonia rejection are still the major problems encountered that hinder its application. Herein, membrane electrochemical reactor (MER) was coupled with MD for simultaneous membrane fouling control and resource recovery. LFL pretreatment with membrane-less electrochemical reactor (EO) and without pretreatment were also purified by MD for comparison. Results showed that the MER-MD system rejected almost all CODCr, total phosphorus, metal salts, and ammonia nitrogen (increased by 33.5%-43.5% without chemical addition), and recovered 31% of ammonia nitrogen and 48% of humic acid in the raw LFL. Owing to the effective removal of hardness (61%) and organics (77%) using MER, the MER-MD system showed higher resistance to the membrane wetting and fouling, with about 61% and 14% higher final vapor flux than those of the MD and EO-MD systems, respectively, and the pure water flux could be fully recovered by alkaline solution cleaning. Moreover, SEM-EDS, ATR-FTIR and XRD characterization further demonstrated the superiority of the MD membrane fouling reversibility of the MER-MD system. Energy consumption and carbon emissions analysis showed that the MER-MD system reduced the total energy consumption/carbon emissions by â¼20% and â¼8% compared to the MD and EO-MD systems, respectively, and the ammonia nitrogen recovered by MER could offset 8.25 kg carbon dioxide equivalent. Therefore, the introduction of MER pretreatment in MD process would be an option to decrease energy consumption and reduce carbon emissions for MD treatment of LFL.
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Amônia , Poluentes Químicos da Água , Amônia/química , Poluentes Químicos da Água/química , Destilação , Nitrogênio , Membranas ArtificiaisRESUMO
Developing light-harvesting materials with broad spectral response is of fundamental importance in full-spectrum solar energy conversion. We found that, when a series of earth-abundant metal (Cu, Co, Ni and Fe) salts are dissolved in coordinating solvents uniformly dispersed nanodots (NDs) are formed rather than fully dissolving as molecular species. The previously unrecognized formation of this condensed state is ascribed to spontaneous aggregation of molecular transition-metal-complexes (TMCs) via weak intermolecular interactions, which results in redshifted and broadened absorption into the NIR region (200-1100â nm). Typical photoredox reactions, such as carbonylation and oxidative dehydrogenation, well demonstrate the feasibility of efficient utilization of NIR light (λ>780â nm) by TMCs NDs. Our finding provides a conceptually new strategy for extending the absorption towards low energy photons in solar energy harvesting and conversion via photoredox transformations.
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Photoelectrochemical (PEC) water splitting is an appealing approach by which to convert solar energy into hydrogen fuel. Polymeric semiconductors have recently attracted intense interest of many scientists for PEC water splitting. The crystallinity of polymer films is regarded as the main factor that determines the conversion efficiency. Herein, potassium poly(heptazine) imide (K-PHI) films with improved crystallinity were in situ prepared on a conductive substrate as a photoanode for solar-driven water splitting. A remarkable photocurrent density of ca. 0.80 mA cm-2 was achieved under air mass 1.5 global illumination without the use of any sacrificial agent, a performance that is ca. 20 times higher than that of the photoanode in an amorphous state, and higher than those of other related polymeric photoanodes. The boosted performance can be attributed to improved charge transfer, which has been investigated using steady state and operando approaches. This work elucidates the pivotal importance of the crystallinity of conjugated polymer semiconductors for PEC water splitting and other advanced photocatalytic applications.
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The development of high efficient photocatalysts for antibiotics contamination in water remains a severe challenge. In this study, a novel step-scheme (S-scheme) photocatalytic heterojunction nanocomposites were fabricated from integrating AgCl nanoparticles on the MIL-100(Fe) octahedron surface through facile multi-stage stirring strategy. The S-scheme heterojunction structure in AgCl/MIL-100(Fe) (AM) nanocomposite provided a more rational utilization of electrons (e-) and holes (h+), accelerated the carrier transport at the junction interface, and enhanced the overall photocatalytic performance of nanomaterials. The visible-light-driven photocatalysts were used to degrade sulfamethazine (SMZ) which attained a high removal efficiency (99.9%). The reaction mechanisms of SMZ degradation in the AM photocatalytic system were explored by electron spin resonance (ESR) and active species capture experiments, which superoxide radical (â¢O2-), hydroxyl radical (â¢OH), and h+ performed as major roles. More importantly, the SMZ degradation pathway and toxicity assessment were proposed. There were four main pathways of SMZ degradation, including the processes of oxidation, hydroxylation, denitrification, and desulfonation. The toxicity of the final products in each pathway was lower than that of the parent according to the toxicity evaluation results. Therefore, this work might provide new insights into the environmentally-friendly photocatalytic processes of S-scheme AM nanocomposites for the efficient degradation of antibiotics pollutants.
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Luz , Sulfametazina , Antibacterianos/química , CatáliseRESUMO
Photocatalytic conversions of C1 molecules under mild conditions have been widely researched in many fields. Adsorption of reactants at a catalyst surface is an indispensable process for C1 conversion and thus it might play a key role in reaction behavior. Herein, for a ZnO sample without photocatalytic activity for CO + H2 reduction, CuO is introduced into ZnO to regulate the adsorption behavior of CO on the CuO-ZnO surface and then to drive the reduction of CO by H2 under UV irradiation. The results of gas sensitivity tests and various in situ characterization methods are as expected. Specifically, surface zinc vacancies and Cu2+ sites at the interface of ZnO and CuO cooperate to construct a special electron-transfer channel (Zn-O-Cu-O) for CO adsorption [CO (ads)]. A new linear adsorption mode of CO at Cu2+ sites occurs, and this successfully changes the electron-transfer behavior of CO (ads) from donating electrons (to ZnO) to accepting electrons (from CuO-ZnO) via electron-transfer channels and d-electrons of Cu2+ matching. Then, CO molecules are reduced by H2 under UV irradiation. The strategy here provides an insight into the design of highly effective catalysts as well as an in-depth understanding of the mechanism of C1 photocatalytic conversion.
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BACKGROUND: In recent years, the goal of universal coverage of the basic medical insurance schemes has been basically achieved in China, but the heavy economic burden of diseases is still the main cause of poverty in many households. Exploring catastrophic health expenditure (CHE) and its inequality are highly important for forward-looking policymaking. This study aims to compare the incidence, intensity and inequality of CHE between urban and rural households in China. METHODS: This study was based on a national representative household survey-the China Family Panel Studies (CFPS)-that was conducted from 2012 to 2018. Concentration index (CI) was employed to measure the inequality of CHE incidence and overshoot, while the decomposition method of the CI was used to estimate the main influencing factors affecting inequality of CHE incidence. RESULTS: From 2012 to 2018, the CHE incidence of urban households increased from 11.01 to 11.88%, while the CHE incidence of rural households decreased from 18.42 to 18.31%. During the same period, the CI of CHE incidence for urban households decreased from - 0.1480 to - 0.1693, while that for rural households declined from - 0.1062 to - 0.1501. The major contribution to the pro-poor inequality in CHE incidence was associated with socioeconomic status, lagged CHE, receiving inpatient services, having elderly members, education of household head, and self-assessed health status of household head. CONCLUSIONS: Rural households had higher risk of incurring CHE than urban households. The strong pro-poor inequality for CHE incidence and overshoot could be found in both two groups. The problem of poverty due to illness was more severe among low-income groups in rural areas than in urban areas. The relevant policy interventions should further focus on encouraging the development of supplementary medical insurance and increasing the reimbursement rate for hospitalization expenses in the medical assistance system.
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Polymeric carbon nitride (PCN) has attracted intensive interest as sustainable, metal-free semiconductor for photoelectrochemical (PEC) water splitting. Charge transfer along the films acts as the main concern to restrict the performance due to the amorphous nature of polymer. Herein, gradient concentration of cobalt disulfide (CoS2 ) merged in PCN films was realized as CSCN photoanode by a one-pot synthesis. Owing to the unique properties of CoS2 , namely high conductivity, the charge transfer of the CSCN photoanode was promoted, and thus the performance for PEC water oxidation was improved. The optimal photoanode exhibited a photoanodic current of 200â µA cm-2 at 1.23â V versus reversible hydrogen electrode under air mass 1.5 global (AM 1.5G) illumination, which was approximately 4 times that of the pristine PCN photoanode. This work provides a new design of metal-free photoanodes to improve the performance of water splitting.
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Sunlight-driven water splitting to produce hydrogen fuel has stimulated intensive scientific interest, as this technology has the potential to revolutionize fossil fuel-based energy systems in modern society. The oxygen evolution reaction (OER) determines the performance of overall water splitting owing to its sluggish kinetics with multielectron transfer processing. Polymeric photocatalysts have recently been developed for the OER, and substantial progress has been realized in this emerging research field. In this Review, the focus is on the photocatalytic technologies and materials of polymeric photocatalysts for the OER. Two practical systems, namely, particle suspension systems and film-based photoelectrochemical systems, form two main sections. The concept is reviewed in terms of thermodynamics and kinetics, and polymeric photocatalysts are discussed based on three key characteristics, namely, light absorption, charge separation and transfer, and surface oxidation reactions. A satisfactory OER performance by polymeric photocatalysts will eventually offer a platform to achieve overall water splitting and other advanced applications in a cost-effective, sustainable, and renewable manner using solar energy.
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Processos Fotoquímicos , Polímeros , Catálise , Luz , Iluminação , OxigênioRESUMO
D-π-A type 4-((9-phenylcarbazol-3-yl)ethynyl)-N-dodecyl-1,8-naphthalimide (CZNI) with a large dipole moment of 8.49â D and A-π-A type bis[(4,4'-1,8-naphthalimide)-N-dodecyl]ethyne (NINI) with a negligible dipole moment of 0.28â D, were smartly designed and synthesized to demonstrate the evidence of a molecular dipole as the dominant mechanism for controlling charge separation of organic semiconductors. In aqueous solution, these two novel naphthalimides can self-assemble to form nanoribbons (NRs) that present significantly different traces of exciton dissociation dynamics. Upon photoexcitation of NINI-NRs, no charge-separated excitons (CSEs) are formed due to the large exciton binding energy, accordingly there is no hydrogen evolution. On the contrary, in the photoexcited CZNI-NRs, the initial bound Frenkel excitons are dissociated to long-lived CSEs after undergoing ultrafast charge transfer within ca. 1.25â ps and charge separation within less than 5.0â ps. Finally, these free electrons were injected into Pt co-catalysts for reducing protons to H2 at a rate of ca. 417â µmol h-1 g-1 , correspondingly an apparent quantum efficiency of ca. 1.3 % can be achieved at 400â nm.
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This work reports the dehydrated Zr-based MOF UiO-66(SH)2 as a visible-light-driven photocatalyst to mimic the biological N2 fixation process. The 15 N2 and other control experiments demonstrated that the new photocatalyst is highly efficient in converting N2 to ammonia. In-situ TGA, XPS, and EXAFS as well as first-principles simulations were used to demonstrate the role of the thermal treatment and the changes of the local structures around Zr due to the dehydration. It was shown that the dehydration opened a gate for the entry of N2 molecules into the [Zr6 O6 ] cluster where the strong N≡N bond was broken stepwise by µ-N-Zr type interactions driven by the photoelectrons aided by the protonation. This mechanism was discussed in comparison with the Lowe-Thorneley mechanism proposed for the MoFe nitrogenase, and with emphasis on the [Zr6 O6 ] cluster effect and the leading role of photoelectrons over the protonation. The results shed new light on understanding the catalytic mechanism of biological N2 fixation and open a new way to fix N2 under mild conditions.
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Fixação de Nitrogênio , Compostos Organometálicos , Desidratação , Humanos , Estruturas Metalorgânicas , Nitrogenase/química , Oxigênio/química , Ácidos Ftálicos , Zircônio/químicaRESUMO
Crystalline covalent organic frameworks (COFs) are porous polymeric semiconductors with network topologies, which are built from the integration of selected organic blocks with covalent bond linkages. They have shown great promise for artificial photosynthesis, owing to broad light harvesting, high crystallinity, and high carrier mobility. This Minireview introduces state-of-the-art COF photocatalysts based on different linkages and discusses the origin of photocatalytic activities for hydrogen evolution. Three typical COF photocatalysts, with linkages including imine (-C=N-), ß-ketoenamine (O=C-C=C-NH-), and vinylene (-C=C-), are discussed with a particular focus on the advancements in synthetic methodologies and structural design, as well as photoelectronic properties that are relevant to photocatalytic performance. The Minireview is expected to elucidate their structure-property relationships and the way to design photoactive COFs with enhanced performances.
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BACKGROUND: After achieving universal basic medical insurance coverage, Chinese government put the development of private health insurance (PHI) on its agenda to further strengthen financial risk protection. This paper aims to assess the level of financial protection that PHI provides for its insured households on the basis of resident basic medical insurance (RBMI). METHODS: We employed balanced panel data collected between 2015 and 2017 from the China Household Finance Survey (CHFS). Catastrophic health expenditure (CHE) and impoverishment due to health spending were applied to measure the financial protection effects. Random effects panel logistic regression model was performed to identify the factors associated with CHE and impoverishment among households covered by RBMI. In the robustness test, the method of propensity score matching (PSM) was employed to solve the problem of endogeneity. RESULTS: From 2015 to 2017, the CHE incidence increased from 12.96 to 14.68 % for all sampled households, while the impoverishment rate decreased slightly from 5.43 to 5.32 % for all sampled households. In 2015, the CHE incidence and impoverishment rate under RBMI + PHI were 4.53 and 0.72 %, respectively, which were lower than those under RBMI alone. A similar phenomenon was observed in 2017. Regression analysis also showed that the households with RBMI + PHI were significantly less likely to experience CHE (marginal effect: -0.054, 95 %CI: -0.075 to -0.034) and impoverishment (marginal effect: -0.049, 95 %CI: -0.069 to -0.028) compared to those with RBMI alone. The results were still robust after using PSM method to eliminate the effects of self-selection on the estimation results. CONCLUSIONS: In the context of universal basic medical insurance coverage, the CHE incidence and impoverishment rate of Chinese households with RBMI were still considerably high in 2015 and 2017. PHI played a positive role in decreasing household financial risk on the basis of RBMI.