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1.
Nat Commun ; 15(1): 7845, 2024 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-39245756

RESUMO

Metal hydrides are crucial intermediates in numerous catalytic reactions. Intensive efforts have been dedicated to constructing molecular metal hydrides, where toxic precursors and delicate mediators are usually involved. Herein, we demonstrate a facile pressure-induced methodology to generate a cost-effective heterogeneous electrocatalytic metal hydride surface for sustainable hydrogen transfer. Taking carbon dioxide (CO2) electroreduction as a model system and zinc (Zn), a well-known carbon monoxide (CO)-selective catalyst, as a model catalyst, we showcase a homogeneous-type hydrogen atom transfer process induced by heterogeneous hydride surfaces, enabling direct hydrogenation pathways traditionally considered "prohibited". Specifically, the maximal Faradaic efficiency for formate is enhanced by ~fivefold to 83% under ambient conditions. Experimental and theoretical analyses reveal that unlike the distal hydrogenation route for CO2 to CO over pristine Zn, the Zn hydride surface enables direct hydrogenation at the carbon site of CO2 to form formate. This work provides a promising material platform for sustainable synthesis.

2.
Adv Mater ; : e2407394, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39148174

RESUMO

Proton exchange membrane water electrolysers promise to usher in a new era of clean energy, but they remain a formidable obstacle in designing active and durable electrocatalysts for the acidic oxygen evolution reaction (OER). In this study, a protonated iridium oxide embedded with single-atom dispersed ruthenium atoms (H3.8Ir1- xRuxO4) that demonstrates exceptional activity and stability in acidic water oxidation is introduced. The single Ru dopants favorably induce localized oxygen vacancies in the Ir─O lattice, synergistically strengthening the adsorption of OOH* intermediates and enhancing the intrinsic OER activity. In addition, the preferential oxidation of Ru and the electronegativity of the oxygen vacancies significantly stabilize the Ir─O active sites, improving the OER stability. Consequently, the H3.8Ir1─ xRuxO4 catalyst shows an overpotential of 255 mV at 10 mA cm-2 and displays exceptional catalytic endurance in acidic electrolytes, surpassing 1100 h, representing a remarkable one-order-of-magnitude increase in stability compared to that of pristine H3.8IrO4. A proton exchange membrane electrolyser utilizing the H3.8Ir1- xRuxO4 catalyst as an anode exhibits stable performance for more than 1280 h under a high current density of 2 A cm-2.

3.
J Ethnopharmacol ; 330: 118196, 2024 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-38631488

RESUMO

ETHNOPHARMACOLOGICAL RELEVANCE: Rosmarinic acid (RA), a natural polyphenol abundant in numerous herbal remedies, has been attracting growing interest owing to its exceptional ability to protect the liver. Toosendanin (TSN), a prominent bioactive compound derived from Melia toosendan Siebold & Zucc., boasts diverse pharmacological properties. Nevertheless, TSN possesses remarkable hepatotoxicity. Intriguingly, the potential of RA to counteract TSN-induced liver damage and its probable mechanisms remain unexplored. AIM OF THE STUDY: This study is aimed at exploring whether RA can alleviate TSN-induced liver injury and the potential mechanisms involved autophagy. MATERIALS AND METHODS: CCK-8 and LDH leakage rate assay were used to evaluate cytotoxicity. Balb/c mice were intraperitoneally administered TSN (20 mg/kg) for 24 h after pretreatment with RA (0, 40, 80 mg/kg) by gavage for 5 days. The autophagic proteins P62 and LC3B expressions were detected using western blot and immunohistochemistry. RFP-GFP-LC3B and transmission electron microscopy were applied to observe the accumulation levels of autophagosomes and autolysosomes. LysoTracker Red and DQ-BSA staining were used to evaluate the lysosomal acidity and degradation ability respectively. Western blot, immunohistochemistry and immunofluorescence staining were employed to measure the expressions of JAK2/STAT3/CTSC pathway proteins. Dual-luciferase reporter gene was used to measure the transcriptional activity of CTSC and RT-PCR was used to detect its mRNA level. H&E staining and serum biochemical assay were employed to determine the degree of damage to the liver. RESULTS: TSN-induced damage to hepatocytes and livers was significantly alleviated by RA. RA markedly diminished the autophagic flux blockade and lysosomal dysfunction caused by TSN. Mechanically, RA alleviated TSN-induced down-regulation of CTSC by activating JAK2/STAT3 signaling pathway. CONCLUSION: RA could protect against TSN-induced liver injury by activating the JAK2/STAT3/CTSC pathway-mediated autophagy and lysosomal function.


Assuntos
Autofagia , Doença Hepática Induzida por Substâncias e Drogas , Cinamatos , Depsídeos , Janus Quinase 2 , Lisossomos , Ácido Rosmarínico , Fator de Transcrição STAT3 , Transdução de Sinais , Animais , Humanos , Masculino , Camundongos , Autofagia/efeitos dos fármacos , Doença Hepática Induzida por Substâncias e Drogas/tratamento farmacológico , Doença Hepática Induzida por Substâncias e Drogas/metabolismo , Doença Hepática Induzida por Substâncias e Drogas/patologia , Doença Hepática Induzida por Substâncias e Drogas/prevenção & controle , Cinamatos/farmacologia , Depsídeos/farmacologia , Medicamentos de Ervas Chinesas/farmacologia , Janus Quinase 2/metabolismo , Fígado/efeitos dos fármacos , Fígado/metabolismo , Fígado/patologia , Lisossomos/efeitos dos fármacos , Lisossomos/metabolismo , Camundongos Endogâmicos BALB C , Transdução de Sinais/efeitos dos fármacos , Fator de Transcrição STAT3/metabolismo
4.
Nat Commun ; 15(1): 3037, 2024 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-38589472

RESUMO

The directional transformation of carbon dioxide (CO2) with renewable hydrogen into specific carbon-heavy products (C6+) of high value presents a sustainable route for net-zero chemical manufacture. However, it is still challenging to simultaneously achieve high activity and selectivity due to the unbalanced CO2 hydrogenation and C-C coupling rates on complementary active sites in a bifunctional catalyst, thus causing unexpected secondary reaction. Here we report LaFeO3 perovskite-mediated directional tandem conversion of CO2 towards heavy aromatics with high CO2 conversion (> 60%), exceptional aromatics selectivity among hydrocarbons (> 85%), and no obvious deactivation for 1000 hours. This is enabled by disentangling the CO2 hydrogenation domain from the C-C coupling domain in the tandem system for Iron-based catalyst. Unlike other active Fe oxides showing wide hydrocarbon product distribution due to carbide formation, LaFeO3 by design is endowed with superior resistance to carburization, therefore inhibiting uncontrolled C-C coupling on oxide and isolating aromatics formation in the zeolite. In-situ spectroscopic evidence and theoretical calculations reveal an oxygenate-rich surface chemistry of LaFeO3, that easily escape from the oxide surface for further precise C-C coupling inside zeolites, thus steering CO2-HCOOH/H2CO-Aromatics reaction pathway to enable a high yield of aromatics.

5.
Food Chem Toxicol ; 187: 114631, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38570025

RESUMO

Toosendanin (TSN) is the main active compound derived from Melia toosendan Sieb et Zucc with various bioactivities. However, liver injury was observed in TSN limiting its clinical application. Lipid metabolism plays a crucial role in maintaining cellular homeostasis, and its disruption is also essential in TSN-induced hepatotoxicity. This study explored the hepatotoxicity caused by TSN in vitro and in vivo. The lipid droplets were significantly decreased, accompanied by a decrease in fatty acid transporter CD36 and crucial enzymes in the lipogenesis including ACC and FAS after the treatment of TSN. It was suggested that TSN caused lipid metabolism disorder in hepatocytes. TOFA, an allosteric inhibitor of ACC, could partially restore cell survival via blocking malonyl-CoA accumulation. Notably, TSN downregulated the LXRα/Lipin1/SREBP1 signaling pathway. LXRα activation improved cell survival and intracellular neutral lipid levels, while SREBP1 inhibition aggravated the cell damage and caused a further decline in lipid levels. Male Balb/c mice were treated with TSN (5, 10, 20 mg/kg/d) for 7 days. TSN exposure led to serum lipid levels aberrantly decreased. Moreover, the western blotting results showed that LXRα/Lipin1/SREBP1 inhibition contributed to TSN-induced liver injury. In conclusion, TSN caused lipid metabolism disorder in liver via inhibiting LXRα/Lipin1/SREBP1 signaling pathway.


Assuntos
Doença Hepática Induzida por Substâncias e Drogas , Medicamentos de Ervas Chinesas , Transtornos do Metabolismo dos Lipídeos , Triterpenos , Camundongos , Animais , Masculino , Metabolismo dos Lipídeos , Medicamentos de Ervas Chinesas/farmacologia , Doença Hepática Induzida por Substâncias e Drogas/etiologia , Lipídeos
6.
Acc Chem Res ; 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38319810

RESUMO

ConspectusLithium-sulfur (Li-S) batteries have attracted worldwide attention as promising next-generation rechargeable batteries due to their high theoretical energy density of 2600 Wh kg-1. The actual energy density of Li-S batteries at the pouch cell level has significantly exceeded that of state-of-the-art Li-ion batteries. However, the overall performances of Li-S batteries under practical working conditions are limited by the sluggish conversion kinetics of the sulfur cathodes. To overcome the above challenge, various kinetic promotion strategies have been proposed to accelerate the multiphase and multi-electron cathodic redox reactions between sulfur, lithium polysulfides (LiPSs), and lithium sulfide. Nowadays, kinetic promoters have been massively employed in sulfur cathodes to achieve Li-S batteries with high energy densities, high rates, and long lifespans. A comprehensive and timely summary of cutting-edge kinetic promoters for sulfur cathodes is of great essence to afford an in-depth understanding of the unique Li-S electrochemistry.In this Account, we outline the recent efforts on the design of sulfur cathode kinetic promoters for advanced Li-S batteries. The latest progress is discussed in detail regarding heterogeneous, homogeneous, and semi-immobilized kinetic promoters. Heterogeneous promoters, representatively known as electrocatalysts, function mainly by reducing the energy barriers of the interfacial electrochemical reactions. The working mechanism, activity regulation strategies, and reconstitution/deactivation processes of the heterogeneous promoters are reviewed to provide guiding principles for rational design. In comparison, homogeneous promoters are able to fully contact with the reaction interfaces and regulate the electron/ion-inaccessible reactants in working Li-S batteries. Redox mediators and redox comediators are typical homogeneous promoters. The former establishes extra chemical reaction pathways to circumvent the originally sluggish steps and boost the overall kinetics, while the latter fundamentally modifies the LiPS molecules to enhance their redox kinetics. For semi-immobilized promoters, the active units are generally anchored on the cathode substrate through flexible chains with mobile characteristics. Such a design endows the promoter with both heterogeneous and homogeneous characteristics to comprehensively regulate the multiphase sulfur redox reactions involving both mobile and immobile reactants.Overall, this Account summarizes the fundamental electrochemistry, design principles, and practical promotion effects of the various kinetic promoters used for the sulfur cathodes in Li-S batteries. We believe that this Account will provide an in-depth and cutting-edge understanding of the unique sulfur electrochemistry, thereby providing guidance for further development of high-performance Li-S batteries and analogous rechargeable battery systems.

7.
J Am Chem Soc ; 145(50): 27531-27538, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-38054906

RESUMO

Single-atom catalysts exhibit promising electrocatalytic activity, a trait that can be further enhanced through the introduction of heteroatom doping within the carbon skeleton. Nonetheless, the intricate relationship between the doping positions and activity remains incompletely elucidated. This contribution sheds light on an inductive effect of single-atom sites, showcasing that the activity of the oxygen reduction reaction (ORR) can be augmented by reducing the spatial gap between the doped heteroatom and the single-atom sites. Drawing inspiration from this inductive effect, we propose a synthesis strategy involving ligand modification aimed at precisely adjusting the distance between dopants and single-atom sites. This precise synthesis leads to optimized electrocatalytic activity for the ORR. The resultant electrocatalyst, characterized by Fe-N3P1 single-atom sites, demonstrates remarkable ORR activity, thus exhibiting great potential in zinc-air batteries and fuel cells.

8.
Angew Chem Int Ed Engl ; 62(48): e202313028, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-37851474

RESUMO

Coordination engineering for single-atom sites has drawn increasing attention, yet its chemical synthesis remains a tough issue, especially for tailorable coordination structures. Herein, a molecular recognition strategy is proposed to fabricate single-atom sites with regulable local coordination structures. Specifically, a heteroatom-containing ligand serves as the guest molecule to induce coordination interaction with the metal-containing host, precisely settling the heteroatoms into the local structure of single-atom sites. As a proof of concept, thiophene is selected as the guest molecule, and sulfur atoms are successfully introduced into the local coordination structure of iron single-atom sites. Ultrahigh oxygen reduction electrocatalytic activity is achieved with a half-wave potential of 0.93 V versus reversible hydrogen electrode. Furthermore, the strategy possesses excellent universality towards diversified types of single-atom sites. This work makes breakthroughs in the fabrication of single-atom sites and affords new opportunities in structural regulation at the atomic level.

9.
Nano Lett ; 23(15): 7046-7053, 2023 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-37470490

RESUMO

Selective electroreduction of CO2 to C1 feed gas provides an attractive avenue to store intermittent renewable energy. However, most of the CO2-to-CO catalysts are designed from the perspective of structural reconstruction, and it is challenging to precisely design a meaningful confining microenvironment for active sites on the support. Herein, we report a local sulfur doping method to precisely tune the electronic structure of an isolated asymmetric nickel-nitrogen-sulfur motif (Ni1-NSC). Our Ni1-NSC catalyst presents >99% faradaic efficiency for CO2-to-CO under a high current density of -320 mA cm-2. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy and differential electrochemical mass spectrometry indicated that the asymmetric sites show a significantly weaker binding strength of *CO and a lower kinetic overpotential for CO2-to-CO. Further theoretical analysis revealed that the enhanced CO2 reduction reaction performance of Ni1-NSC was mainly due to the effectively decreased intermediate activation energy.

10.
Nat Commun ; 14(1): 2137, 2023 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-37059857

RESUMO

The removal of acetylene impurities remains important yet challenging to the ethylene downstream industry. Current thermocatalytic semihydrogenation processes require high temperature and excess hydrogen to guarantee complete acetylene conversion. For this reason, renewable electricity-based electrocatalytic semihydrogenation of acetylene over Cu-based catalysts is an attractive route compared to the energy-intensive thermocatalytic processes. However, active Cu electrocatalysts still face competition from side reactions and often require high overpotentials. Here, we present an undercoordinated Cu nanodots catalyst with an onset potential of -0.15 V versus reversible hydrogen electrode that can exclusively convert C2H2 to C2H4 with a maximum Faradaic efficiency of ~95.9% and high intrinsic activity in excess of -450 mA cm-2 under pure C2H2 flow. Subsequently, we successfully demonstrate simulated crude ethylene purification, continuously producing polymer-grade C2H4 with <1 ppm C2H2 for 130 h at a space velocity of 1.35 × 105 ml gcat-1 h-1. Theoretical calculations and in situ spectroscopies reveal a lower energy barrier for acetylene semihydrogenation over undercoordinated Cu sites than nondefective Cu surface, resulting in the excellent C2H2-to-C2H4 catalytic activity of Cu nanodots.

11.
J Am Chem Soc ; 145(11): 6057-6066, 2023 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-36888741

RESUMO

The development of efficient photocatalysts for N2 fixation to produce NH3 under ambient conditions remains a great challenge. Since covalent organic frameworks (COFs) possess predesignable chemical structures, good crystallinity, and high porosity, it is highly significant to explore their potential for photocatalytic nitrogen conversion. Herein, we report a series of isostructural porphyrin-based COFs loaded with Au single atoms (COFX-Au, X = 1-5) for photocatalytic N2 fixation. The porphyrin building blocks act as the docking sites to immobilize Au single atoms as well as light-harvesting antennae. The microenvironment of the Au catalytic center is precisely tuned by controlling the functional groups at the proximal and distal positions of porphyrin units. As a result, COF1-Au decorated with strong electron-withdrawing groups exhibits a high activity toward NH3 production with rates of 333.0 ± 22.4 µmol g-1 h-1 and 37.0 ± 2.5 mmol gAu-1 h-1, which are 2.8- and 171-fold higher than that of COF4-Au decorated with electron-donating functional groups and a porphyrin-Au molecular catalyst, respectively. The NH3 production rates could be further increased to 427.9 ± 18.7 µmol g-1 h-1 and 61.1 ± 2.7 mmol gAu-1 h-1 under the catalysis of COF5-Au featuring two different kinds of strong electron-withdrawing groups. The structure-activity relationship analysis reveals that the introduction of electron-withdrawing groups facilitates the separation and transportation of photogenerated electrons within the entire framework. This work manifests that the structures and optoelectronic properties of COF-based photocatalysts can be finely tuned through a rational predesign at the molecular level, thus leading to superior NH3 evolution.

12.
Nat Commun ; 14(1): 354, 2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36681684

RESUMO

Heteroatom-doping is a practical means to boost RuO2 for acidic oxygen evolution reaction (OER). However, a major drawback is conventional dopants have static electron redistribution. Here, we report that Re dopants in Re0.06Ru0.94O2 undergo a dynamic electron accepting-donating that adaptively boosts activity and stability, which is different from conventional dopants with static dopant electron redistribution. We show Re dopants during OER, (1) accept electrons at the on-site potential to activate Ru site, and (2) donate electrons back at large overpotential and prevent Ru dissolution. We confirm via in situ characterizations and first-principle computation that the dynamic electron-interaction between Re and Ru facilitates the adsorbate evolution mechanism and lowers adsorption energies for oxygen intermediates to boost activity and stability of Re0.06Ru0.94O2. We demonstrate a high mass activity of 500 A gcata.-1 (7811 A gRe-Ru-1) and a high stability number of S-number = 4.0 × 106 noxygen nRu-1 to outperform most electrocatalysts. We conclude that dynamic dopants can be used to boost activity and stability of active sites and therefore guide the design of adaptive electrocatalysts for clean energy conversions.


Assuntos
Rênio , Rutênio , Adsorção , Óxidos , Oxigênio
13.
Adv Mater ; 35(7): e2209233, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36414611

RESUMO

Dilute alloying is an effective strategy to tune properties of solid catalysts but is rarely leveraged in complex reactions beyond small molecule conversion. In this work, dilute dopants are demonstrated to serve as activating centers to construct multiatom catalytic domains in metal nitride electrocatalysts for lithium-sulfur (Li-S) batteries, of which the sulfur cathode suffers from sluggish and complex conversion reactions. With titanium nitride (TiN) as a model system, the dilute cobalt alloying is shown to greatly improve the reaction kinetics while inducing negligible catalyst reconstruction. Compared to the pristine TiN, the dilute nitride alloy catalyst enables onefold increase in the high rate (2.0 C) capacities of Li-S batteries, as well as an impressively low cyclic decay rate of 0.17% at a sulfur loading of 4.0 mgS cm-2 . This work opens up new opportunities toward the rational design of Li-S electrocatalysts by dilute alloying and also enlightens the understandings of complex domain-catalyzed reactions in energy applications.

14.
Angew Chem Int Ed Engl ; 61(48): e202214037, 2022 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-36214644

RESUMO

The development of emerging rechargeable batteries is often hindered by limited chemical understanding composing of entangled patterns in an enormous space. Herein, we propose an interpretable hybrid machine learning framework to untangle intractable degradation chemistries of conversion-type batteries. Rather than being a black box, this framework not only demonstrates an ability to accurately forecast lithium-sulfur batteries (with a test mean absolute error of 8.9 % for the end-of-life prediction) but also generate useful physical understandings that illuminate future battery design and optimization. The framework also enables the discovery of a previously unknown performance indicator, the ratio of electrolyte amount to high-voltage-region capacity at the first discharge, for lithium-sulfur batteries complying practical merits. The present data-driven approach is readily applicable to other energy storage systems due to its versatility and flexibility in modules and inputs.

15.
Angew Chem Int Ed Engl ; 61(52): e202211448, 2022 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-36314993

RESUMO

Lithium-sulfur (Li-S) battery is strongly considered as one of the most promising energy storage systems due to its high theoretical energy density and low cost. However, the sluggish reduction kinetics from Li2 S4 to Li2 S during discharge hinders the practical application of Li-S batteries. Although various electrocatalysts have been proposed to improve the reaction kinetics, the electrocatalytic mechanism is unclear due to the complexity of sulfur reduction reactions (SRR). It is crucial to understand the electrocatalytic mechanism thoroughly for designing advanced electrocatalysts. Herein an electrocatalytic model is constructed to reveal the chemical mechanism of the SRR in Li-S batteries based on systematical density functional theory calculations, taking heteroatoms-doped carbon materials as an example. The adsorption energy of LiSy ⋅ (y=1, 2, or 3) radicals is used as a key descriptor to predict the reaction pathway, rate-determining step, and overpotential. A diagram for designing advanced electrocatalysts is accordingly constructed. This work establishes a theoretical model, which is an intelligent integration for probing the complicated SRR mechanisms and designing advanced electrocatalysts for high-performance Li-S batteries.

16.
Nat Commun ; 13(1): 5567, 2022 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-36138013

RESUMO

Spontaneous monodispersion of reducible active species (e.g., Fe, Co) and their stabilization in reductive atmospheres remain a key challenge in catalytic syngas chemistry. In this study, we present a series of catalysts including spontaneously monodispersed and enriched Fe on ZnCr2O4. Deep investigation shows remarkable performance in the syngas-to-aromatic reaction only when monodispersed Fe coupled with a H-ZSM-5 zeolite. Monodispersed Fe increases the turnover frequency from 0.14 to 0.48 s-1 without sacrificing the record high selectivity of total aromatics (80-90%) at a single pass. The increased activity is ascribed to more efficient activation of CO and H2 at oxygen vacancy nearest to the isolated Fe site and the prevention of carbide formation. Atomic precise characterization and theoretical calculations shed light on the origin and implications of spontaneous Fe monodispersion, which provide guidance to the design of next-generation catalyst for upgrading small molecules to synthetic fuels and chemicals.

17.
Angew Chem Int Ed Engl ; 61(29): e202204776, 2022 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-35575049

RESUMO

The lifespan of practical lithium (Li)-metal batteries is severely hindered by the instability of Li-metal anodes. Fluorinated solid electrolyte interphase (SEI) emerges as a promising strategy to improve the stability of Li-metal anodes. The rational design of fluorinated molecules is pivotal to construct fluorinated SEI. Herein, design principles of fluorinated molecules are proposed. Fluoroalkyl (-CF2 CF2 -) is selected as an enriched F reservoir and the defluorination of the C-F bond is driven by leaving groups on ß-sites. An activated fluoroalkyl molecule (AFA), 2,2,3,3-tetrafluorobutane-1,4-diol dinitrate is unprecedentedly proposed to render fast and complete defluorination and generate uniform fluorinated SEI on Li-metal anodes. In Li-sulfur (Li-S) batteries under practical conditions, the fluorinated SEI constructed by AFA undergoes 183 cycles, which is three times the SEI formed by LiNO3 . Furthermore, a Li-S pouch cell of 360 Wh kg-1 delivers 25 cycles with AFA. This work demonstrates rational molecular design principles of fluorinated molecules to construct fluorinated SEI for practical Li-metal batteries.

18.
Nat Commun ; 13(1): 1399, 2022 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-35302055

RESUMO

The electrochemical conversion of carbon di-/monoxide into commodity chemicals paves a way towards a sustainable society but it also presents one of the great challenges in catalysis. Herein, we present the trends in selectivity towards specific dicarbon oxygenate/hydrocarbon products from carbon monoxide reduction on transition metal catalysts, with special focus on copper. We unveil the distinctive role of electrolyte pH in tuning the dicarbon oxygenate/hydrocarbon selectivity. The understanding is based on density functional theory calculated energetics and microkinetic modeling. We identify the critical reaction steps determining selectivity and relate their transition state energies to two simple descriptors, the carbon and hydroxide binding strengths. The atomistic insight gained enables us to rationalize a number of experimental observations and provides avenues towards the design of selective electrocatalysts for liquid fuel production from carbon di-/monoxide.

19.
ACS Appl Mater Interfaces ; 13(44): 52044-52054, 2021 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-34415714

RESUMO

Tuning bimetallic effects is a promising strategy to guide catalytic properties. However, the nature of these effects can be difficult to assess and compare due to the convolution with other factors such as the catalyst surface structure and morphology and differences in testing environments. Here, we investigate the impact of atomic-scale bimetallic effects on the electrochemical CO2 reduction performance of Cu-based catalysts by leveraging a systematic approach that unifies protocols for materials synthesis and testing and enables accurate comparisons of intrinsic catalytic activity and selectivity. We used the same physical vapor deposition method to epitaxially grow Cu(100) films decorated with a small amount of noble or base metal atoms and a combination of experimental characterization and first-principles calculations to evaluate their physicochemical and catalytic properties. The results indicate that the metal atoms segregate to under-coordinated Cu sites during physical vapor deposition, suppressing CO reduction to oxygenates and hydrocarbons and promoting competing pathways to CO, formate, and hydrogen. Leveraging these insights, we rationalize bimetallic design principles to improve catalytic selectivity for CO2 reduction to CO, formate, oxygenates, or hydrocarbons. Our study provides one of the most extensive studies on Cu bimetallics for CO2 reduction, establishing a systematic approach that is broadly applicable to research in catalyst discovery.

20.
Ying Yong Sheng Tai Xue Bao ; 32(6): 2089-2097, 2021 Jun.
Artigo em Chinês | MEDLINE | ID: mdl-34212615

RESUMO

Vegetation phenology, a regular and periodic phenomenon in nature, is an important indicator for natural environment, especially climate change. The study of spatiotemporal variations of vegetation phenology is of great significance for monitoring the changes of terrestrial vegetation. In this study, the Savitzky-Golay (S-G) filtering method was used to reconstruct time-series MODIS enhanced vegetation index (EVI) data in the Qinling Mountains from 2001 to 2018. The dynamic threshold method was used to extract the spring phenological parameter (start of growth season, SOS). The correlation between multi-year mean SOS and interannual variation with altitude and slope was analyzed. The results showed that SOS was delayed by 1.82 d with every 100 m increase in altitude in the Qinling Mountains. The interannual change trends of SOS mainly concentrated in 0-5 d·(10 a)-1. The pixels with delaying trend were mainly distributed in low-altitude regions, with the delaying degree being gradually decreased with the elevation. The interannual change trend of SOS in high-altitude regions was more complex than that in lower-altitude regions. The multi-year average SOS in the northern slope was approximately 2.9 d earlier than that of the southern slope, whereas the southern slope had a more significant advancing trend. The interannual change trends of SOS in both north and south slopes showed a delaying trend in low-altitude, with little difference between north and south slopes. The advancing trend in middle and high altitude was significantly different.


Assuntos
Altitude , Mudança Climática , China , Estações do Ano , Temperatura
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