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1.
Conversion of syngas (CO, H2) to hydrocarbons, commonly known as the Fischer–Tropsch (FT) synthesis, represents a fundamental pillar in today's chemical industry and is typically carried out under technically demanding conditions (1–3 MPa, 300–400 °C). Photocatalysis using sunlight offers an alternative and potentially more sustainable approach for the transformation of small molecules (H2O, CO, CO2, N2, etc.) to high‐valuable products, including hydrocarbons. Herein, a novel series of Fe‐based heterostructured photocatalysts (Fe‐x) is successfully fabricated via H2 reduction of ZnFeAl‐layered double hydroxide (LDH) nanosheets at temperatures (x) in the range 300–650 °C. At a reduction temperature of 500 °C, the heterostructured photocatalyst formed (Fe‐500) consists of Fe0 and FeOx nanoparticles supported by ZnO and amorphous Al2O3. Fe‐500 demonstrates remarkable CO hydrogenation performance with very high initial selectivities toward hydrocarbons (89%) and especially light olefins (42%), and a very low selectivity towards CO2 (11%). The intimate and abundant interfacial contacts between metallic Fe0 and FeOx in the Fe‐500 photocatalyst underpins its outstanding photocatalytic performance. The photocatalytic production of high‐value light olefins with suppressed CO2 selectivity from CO hydrogenation is demonstrated here.  相似文献   

2.
The selective hydrogenation of acetylene to ethylene in an ethylene‐rich gas stream is an important process in the chemical industry. Pd‐based catalysts are widely used in this reaction due to their excellent hydrogenation activity, though their selectivity for acetylene hydrogenation and durability need improvement. Herein, the successful synthesis of atomically dispersed Pd single‐atom catalysts on nitrogen‐doped graphene (Pd1/N‐graphene) by a freeze‐drying‐assisted method is reported. The Pd1/N‐graphene catalyst exhibits outstanding activity and selectivity for the hydrogenation of C2H2 with H2 in the presence of excess C2H4 under photothermal heating (UV and visible‐light irradiation from a Xe lamp), achieving 99% conversion of acetylene and 93.5% selectivity to ethylene at 125 °C. This remarkable catalytic performance is attributed to the high concentration of Pd active sites on the catalyst surface and the weak adsorption energy of ethylene on isolated Pd atoms, which prevents C2H4 hydrogenation. Importantly, the Pd1/N‐graphene catalyst exhibits excellent durability at the optimal reaction temperature of 125 °C, which is explained by the strong local coordination of Pd atoms by nitrogen atoms, which suppresses the Pd aggregation. The results presented here encourage the wider pursuit of solar‐driven photothermal catalyst systems based on single‐atom active sites for selective hydrogenation reactions.  相似文献   

3.
A series of novel CoFe‐based catalysts are successfully fabricated by hydrogen reduction of CoFeAl layered‐double‐hydroxide (LDH) nanosheets at 300–700 °C. The chemical composition and morphology of the reaction products (denoted herein as CoFe‐x) are highly dependent on the reduction temperature (x). CO2 hydrogenation experiments are conducted on the CoFe‐x catalysts under UV–vis excitation. With increasing LDH‐nanosheet reduction temperature, the CoFe‐x catalysts show a progressive selectivity shift from CO to CH4, and eventually to high‐value hydrocarbons (C2+). CoFe‐650 shows remarkable selectivity toward hydrocarbons (60% CH4, 35% C2+). X‐ray absorption fine structure, high‐resolution transmission electron microscopy, Mössbauer spectroscopy, and density functional theory calculations demonstrate that alumina‐supported CoFe‐alloy nanoparticles are responsible for the high selectivity of CoFe‐650 for C2+ hydrocarbons, also allowing exploitation of photothermal effects. This study demonstrates a vibrant new catalyst platform for harnessing clean, abundant solar‐energy to produce valuable chemicals and fuels from CO2.  相似文献   

4.
Catalysts with low‐cost, high activity and stability toward oxygen reduction reaction (ORR) are extremely desirable, but its development still remains a great challenge. Here, a novel magnetically separable hybrid of multimetal oxide, cobalt ferrite (CoFe2O4), anchored on nitrogen‐doped reduced graphene oxide (CoFe2O4/NG) is prepared via a facile solvothermal method followed by calcination at 500 °C. The structure of CoFe2O4/NG and the interaction of both components are analyzed by several techniques. The possible formation of Co/Fe N interaction in the CoFe2O4/NG catalyst is found. As a result, the well‐combination of CoFe2O4 nanoparticles with NG and its improved crystallinity lead to a synergistic and efficient catalyst with high performance to ORR through a four‐electron‐transfer process in alkaline medium. The CoFe2O4/NG exhibits particularly comparable catalytic activity as commercial Pt/C catalyst, and superior stability against methanol oxidation and CO poisoning. Meanwhile, it has been proved that both nitrogen doping and the spinel structure of CoFe2O4 can have a significant contribution to the catalytic activity by contrast experiments. Multimetal oxide hybrid demonstrates better catalysis to ORR than a single metal oxide hybrid. All results make the low‐cost and magnetically separable CoFe2O4/NG a promising alternative for costly platinum‐based ORR catalyst in fuel cells and metal‐air batteries.  相似文献   

5.
Upcoming emission regulations order highly effective NOx‐reduction systems in lean‐burn engines requiring new catalytic materials and integrated control of the reduction process. Thus, new approaches for NOx‐reduction and its monitoring over an On‐Board‐Diagnostic (OBD) system are suggested throughout the globe. A promising attempt is the development of a catalytic system having an integrated NOx‐sensor, based on selective catalytic reduction process and impedance sensors. The study displays the results achieved both with a perovskite type of self‐regenerative catalyst functioning by H2‐reductant and with impedance NOx‐sensors. The catalysts were tested at the temperature range of 150 °C to 360 °C yielding NOx conversion rates of 92 % with high selectivity to N2. Impedance sensors having NiCr2O4‐ and NiO‐SE and PYSZ‐ and FYSZ‐electrolytes are developed and tested at 600 °C under lean atmosphere (5 vol. % O2). Better sensing behaviour towards NO and lower cross‐selectivity towards O2, CO, CO2 and CH4 have been observed with sensors having NiO‐SE.  相似文献   

6.
Hydrogen peroxide (H2O2) is a green oxidizer widely involved in a vast number of chemical reactions. Electrochemical reduction of oxygen to H2O2 constitutes an environmentally friendly synthetic route. However, the oxygen reduction reaction (ORR) is kinetically sluggish and undesired water serves as the main product on most electrocatalysts. Therefore, electrocatalysts with high reactivity and selectivity are highly required for H2O2 electrosynthesis. In this work, a synergistic strategy is proposed for the preparation of H2O2 electrocatalysts with high ORR reactivity and high H2O2 selectivity. A Co?Nx?C site and oxygen functional group comodified carbon‐based electrocatalyst (named as Co–POC–O) is synthesized. The Co–POC–O electrocatalyst exhibits excellent catalytic performance for H2O2 electrosynthesis in O2‐saturated 0.10 m KOH with a high selectivity over 80% as well as very high reactivity with an ORR potential at 1 mA cm?2 of 0.79 V versus the reversible hydrogen electrode (RHE). Further mechanism study identifies that the Co?Nx?C sites and oxygen functional groups contribute to the reactivity and selectivity for H2O2 electrogeneration, respectively. This work affords not only an emerging strategy to design H2O2 electrosynthesis catalysts with remarkable performance, but also the principles of rational combination of multiple active sites for green and sustainable synthesis of chemicals through electrochemical processes.  相似文献   

7.
The tumor microenvironment (TME) has been increasingly recognized as a crucial contributor to tumorigenesis. Based on the unique TME for achieving tumor‐specific therapy, here a novel concept of photothermal‐enhanced sequential nanocatalytic therapy in both NIR‐I and NIR‐II biowindows is proposed, which innovatively changes the condition of nanocatalytic Fenton reaction for production of highly efficient hydroxyl radicals (?OH) and consequently suppressing the tumor growth. Evidence suggests that glucose plays a vital role in powering cancer progression. Encouraged by the oxidation of glucose to gluconic acid and H2O2 by glucose oxidase (GOD), an Fe3O4/GOD‐functionalized polypyrrole (PPy)‐based composite nanocatalyst is constructed to achieve diagnostic imaging‐guided, photothermal‐enhanced, and TME‐specific sequential nanocatalytic tumor therapy. The consumption of intratumoral glucose by GOD leads to the in situ elevation of the H2O2 level, and the integrated Fe3O4 component then catalyzes H2O2 into highly toxic ?OH to efficiently induce cancer‐cell death. Importantly, the high photothermal‐conversion efficiency (66.4% in NIR‐II biowindow) of the PPy component elevates the local tumor temperature in both NIR‐I and NIR‐II biowindows to substaintially accelerate and improve the nanocatalytic disproportionation degree of H2O2 for enhancing the nanocatalytic‐therapeutic efficacy, which successfully achieves a remarkable synergistic anticancer outcome with minimal side effects.  相似文献   

8.
Value‐added aromatic monomers such as benzene, toluene, and xylenes (BTX) are very important building‐block chemicals for the production of plastics, polymers, solvents, pesticides, dyes, and adhesives. Syngas‐to‐aromatics (STA) is a very promising approach for the synthesis of aromatic monomers, and is catalyzed via bifunctional catalysts in a single reactor, wherein methanol/dimethyl ether and/or olefins intermediates formed from syngas on metal components are converted into aromatic monomers exclusively on the HZSM‐5 by cascade reactions. Since an optimal Fischer–Tropsch synthesis (FTS) temperature of Fe‐based catalysts is very close to an aromatization temperature of HZSM‐5, Fe‐based catalysts have been frequently used/modified for the synthesis of aromatic monomers from hydrogenation of carbon oxides (CO and CO2). The nature of metal components and amounts of Brönsted acid sites on HZSM‐5, and their mesoporosity and intimacy, significantly alter the selectivity for aromatics by tuning BTX distibution and catalyst stability. Although many developments have been achieved regarding the STA process in recent years, no reviews have been published in this flourishing research area over the last two decades. Here, the recent advances and forthcoming challenges in the progress of syngas (CO+H2) chemistry and hydrogenation of CO2 toward the value‐added aromatic monomers through cascade reactions are highlighted.  相似文献   

9.
Titanium dioxide (TiO2) has been widely investigated and used in many areas due to its high refractive index and ultraviolet light absorption, but the lack of absorption in the visible–near infrared (Vis–NIR) region limits its application. Herein, multifunctional Fe@γ‐Fe2O3@H‐TiO2 nanocomposites (NCs) with multilayer‐structure are synthesized by one‐step hydrogen reduction, which show remarkably improved magnetic and photoconversion effects as a promising generalists for photocatalysis, bioimaging, and photothermal therapy (PTT). Hydrogenation is used to turn white TiO2 in to hydrogenated TiO2 (H‐TiO2), thus improving the absorption in the Vis–NIR region. Based on the excellent solar‐driven photocatalytic activities of the H‐TiO2 shell, the Fe@γ‐Fe2O3 magnetic core is introduced to make it convenient for separating and recovering the catalytic agents. More importantly, Fe@γ‐Fe2O3@H‐TiO2 NCs show enhanced photothermal conversion efficiency due to more circuit loops for electron transitions between H‐TiO2 and γ‐Fe2O3, and the electronic structures of Fe@γ‐Fe2O3@H‐TiO2 NCs are calculated using the Vienna ab initio simulation package based on the density functional theory to account for the results. The reported core–shell NCs can serve as an NIR‐responsive photothermal agent for magnetic‐targeted photothermal therapy and as a multimodal imaging probe for cancer including infrared photothermal imaging, magnetic resonance imaging, and photoacoustic imaging.  相似文献   

10.
Biomass is the most abundant renewable resource on earth and developing high‐performance nonprecious selective hydrogenation (SH) catalysts will enable the use of biomass to replace rapidly diminishing fossil resources. This work utilizes ZIF‐67‐derived nitrogen‐doped carbon nanotubes to confine Co nanoparticles (NPs) with Co–Nx active sites as a high‐performance SH catalyst. The confined Co NPs with Co–Nx exhibit excellent catalytic activity, selectivity, and stability toward a wide range of biomass‐derived compounds. Such active sites can selectively hydrogenate aldehyde, ketone, carboxyl, and nitro groups of biomass‐derived compounds into value‐added fine chemicals with 100% selectivity. The reported approach could be adopted to create other forms of catalytically active sites from other nonprecious metals.  相似文献   

11.
Chemodynamic therapy (CDT) has attracted considerable attention recently, but the poor reaction kinetics restrict its practical utility in clinic. Herein, glucose oxidase (GOx) functionalized ancient pigment nanosheets (SrCuSi4O10, SC) for programmable near‐infrared II (NIR‐II) photothermal‐enhanced starvation primed CDT is developed. The SC nanosheets (SC NSs) are readily exfoliated from SC bulk suspension in water and subsequently functionalized with GOx to form the nanocatalyst (denoted as SC@G NSs). Upon laser irradiation, the photothermal effect of SC NSs can enhance the catalytic activity of GOx for NIR‐II photothermal‐enhanced starvation therapy, which effectively eliminates intratumoral glucose and produces abundant hydrogen peroxide (H2O2). Importantly, the high photothermal‐conversion efficiency (46.3%) of SC@G NSs in second biological window permits photothermal therapy of deep‐seated tumors under the guidance of NIR‐II photoacoustic imaging. Moreover, the acidity amplification due to gluconic acid generation will in turn accelerate the degradation of SC NSs, facilitating the release of strontium (Sr) and copper (Cu) ions. Both the elevated H2O2 and the released ions will prime the Cu2+/Sr2+‐H2O2 reaction for enhanced CDT. Thus, a programmable NIR‐II photothermal‐enhanced starvation primed CDT is established to combat cancer with minimal side effects.  相似文献   

12.
The increase of reaction temperature of electrocatalysts is regarded as an efficient method to improve the oxygen evolution reaction (OER) activity. Herein, it is reported that the electrocatalytic performance of dual functional (i.e., electrocatalytic and photothermal functions) Co3O4 can be dramatically improved via its photothermal effect. The operating temperature of the Co3O4 electrode is elevated in situ under near infrared (NIR) light irradiation, resulting in enhanced oxygen evolution activity due to its accelerated electrical conductivity, reaction kinetics, and desorption rate of O2 bubbles from the electrode. In addition, photothermal effect can also enhance the electrocatalytic reaction rates of metal‐doped Co3O4 electrodes, indicating that it is able to significantly improve the OER activities of electrodes together with other modification strategies. With the assistance of the photothermal effect, the obtained Ni‐doped Co3O4 catalyst requires an extremely low overpotential of 208 mV to achieve a benchmark of 10 mA cm?2 with a small Tafel slope, superior to most reported Co‐based catalysts. Significantly, the electrocatalytic performance of other electrodes with photothermal effect, such as CoN, CoP, and CoS, are also boosted under NIR light irradiation, indicating opportunities for implementing photothermal enhancement in electrocatalytic water splitting.  相似文献   

13.
Rational design of complex metal–organic framework (MOF) hybrid precursors offers a great opportunity to construct various functional nanostructures. Here, a novel MOF‐hybrid‐assisted strategy to synthesize Co3O4/Co‐Fe oxide double‐shelled nanoboxes is reported. In the first step, zeolitic imidazolate framework‐67 (ZIF‐67, a Co‐based MOF)/Co‐Fe Prussian blue analogue (PBA) yolk–shell nanocubes are formed via a facile anion‐exchange reaction between ZIF‐67 nanocube precursors and [Fe(CN)6]3? ions at room temperature. Subsequently, an annealing treatment is applied to prepare Co3O4/Co‐Fe oxide double‐shelled nanoboxes. Owing to the structural and compositional benefits, the as‐derived Co3O4/Co‐Fe oxide double‐shelled nanoboxes exhibit enhanced electrocatalytic performance for oxygen evolution reaction in alkaline solution.  相似文献   

14.
The implementation of water splitting systems, powered by sustainable energy resources, appears to be an attractive strategy for producing high‐purity H2 in the absence of the release of carbon dioxide (CO2). However, the high cost, impractical operating conditions, and unsatisfactory efficiency and stability of conventional methods restrain their large‐scale development. Seawater covers 70% of the Earth's surface and is one of the most abundant natural resources on the planet. New research is looking into the possibility of using seawater to produce hydrogen through electrolysis and will provide remarkable insight into sustainable H2 production, if successful. Here, guided by density functional theory (DFT) calculations to predict the selectivity of gas‐evolving catalysts, a seawater‐splitting device equipped with affordable state‐of‐the‐art electrocatalysts composed of earth‐abundant elements (Fe, Co, Ni, and Mo) is demonstrated. This device shows excellent durability and specific selectivity toward the oxygen evolution reaction in seawater with near 100% Faradaic efficiency for the production of H2 and O2. Powered by a single commercial III–V triple‐junction photovoltaic cell, the integrated system achieves spontaneous and efficient generation of high‐purity H2 and O2 from seawater at neutral pH with a remarkable 17.9% solar‐to‐hydrogen efficiency.  相似文献   

15.
Overproduced hydrogen sulfide (H2S) is of vital importance for the progress of colon cancer and promotes cancer cellular proliferation. Devising pharmacological nanomaterials for tumor‐specific H2S activation will be significant for precise colon cancer treatment. Herein, a biocompatible fusiform iron oxide‐hydroxide nanospindles (FeOOH NSs) nanosystem for magnetic resonance imaging (MRI), ferroptosis, and H2S based cascade reaction‐enhanced combinational colon cancer treatment is developed. The FeOOH NSs can effectively scavenge endogenous H2S via the reduction reaction to prohibit the growth of CT26 colon cancer. The cascade produced FeS driven by overexpressed H2S exhibits near‐infrared‐triggered photothermal therapy capability and Fe2+‐mediated ferroptosis functionality. Meanwhile, the as‐prepared FeOOH NSs can light up tumor tissues as a potent MRI contrast agent. Additionally, FeOOH NSs present desirable biosafety in a murine model for up to three months and avoid any long‐term toxicity. Furthermore, it is found that these H2S‐responsible nanotheranostics do not cause any cure effects on other cancer types, such as 4T1 breast cancer. Overall, the findings illustrate that the biocompatible FeOOH NSs can be successfully employed as a theranostic for specifically treating colon cancer, which may promote the clinical translation and development of H2S‐responsive nanoplatforms.  相似文献   

16.
Single‐atom Co catalyst Co‐Tpy‐C with well‐defined sites is synthesized by pyrolysis of a Co terpyridine (Tpy) organometallic complex. The Co‐Tpy‐C catalyst exhibits excellent activity for the electrochemical CO2 reduction reaction in aqueous electrolyte, with CO faradaic efficiency (FE) of over 95% from ?0.7 to ?1.0 V (vs RHE). By comparison, catalysts without Co or Tpy ligand added do not show any high CO FE. When simulated flue gas with 15% of CO2 is used as the source of CO2, CO FE is kept at 90.1% at ?0.5 V versus RHE. During gas phase flow electrolysis using simulated flue gas, the CO partial current density is further increased to 86.4 mA cm?2 and CO FE reached >90% at the cell voltage of 3.4 V. Experiments and density functional theory calculations indicate that uniform single‐atom Co–N4 sites mainly contribute to the high activity for CO2 reduction.  相似文献   

17.
The catalytic behavior of transition metals (Sc to Zn) combined in polymeric phthalocyanine (Pc) is investigated systematically by using first‐principles calculations. The results indicate that CoPc exhibits the highest catalytic activity for CO oxidation at room temperature with low energy barriers. By exploring the two well‐established mechanisms for CO oxidation with O2, namely, the Langmuir–Hinshelwood (LH) and the Eley–Rideal (ER) mechanisms, it is found that the first step of CO oxidation catalyzed by CoPc is the LH mechanism (CO + O2 → CO2 + O) with energy barrier as low as 0.65 eV. The second step proceeds via both ER and LH mechanisms (CO + O → CO2) with small energy barriers of 0.10 and 0.12 eV, respectively. The electronic resonance among Co‐3d, CO‐2π*, and O2‐2π* orbitals is responsible for the high activity of CoPc. These results have significant implications for a novel avenue to fabricate organometallic sheet nanocatalysts for CO oxidation with low cost and high activity.  相似文献   

18.
Copper sulfides (Cu2–xS), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu2‐xS nanocrystals (NCs) is a top priority for further energy‐and sustainability relevant nanodevices. Here, a shape‐controlled high quality Cu7S4 NCs synthesis strategy is reported using sulfur in 1‐octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu7S4 NCs is further explored for light‐driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as‐synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk‐like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu7S4 NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%.  相似文献   

19.
It is highly desired but challenging to design high performance catalyst for selective hydrogenation of nitro compounds into amino compounds. Herein, a boosting chemoselective hydrogenation strategy on Pt@Fe2O3 is proposed with gradient oxygen vacancy by synergy of hydrogen spillover and preferential adsorption. Experimental and theoretical investigations reveal that the nitro is preferentially adsorbed onto oxygen vacancy of Pt@Fe2O3, meanwhile, the H2 dissociated on Pt nanoparticles and then spillover to approach the nitro for selective hydrogenation (>99% conversion of 4-nitrostyrene, > 99% selectivity of 4-aminostyrene, TOF of 2351 h−1). Moreover, the iron oxide support endows the catalyst magnetic retrievability. This high activity, selectivity, and easy recovery strategy provide a promising avenue for selective hydrogenation catalysis of various nitroaromatic.  相似文献   

20.
Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH4Cl, and Co(NO3)2·6H2O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m2 g?1), and homogeneous distribution of active sites (C–N, Co–Nx, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO3)2·6H2O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm?2.  相似文献   

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