Hydrochar-Supported NiFe2O4Nanosheets with a Tailored Microstructure for Enhanced CO2Photoreduction to Syngas.

Constructing high-efficiency composite photocatalysts with enhanced charge transfer and a rapid surface catalytic reaction has recently received significant attention. Herein, a hydrochar-mediated NiFe2O4 nanosheet (C/NFO) composite was rationally constructed by a simple hydrothermal method. Intimate interface contacts and chemical interactions between hydrochar and NFO were formed. The prepared C/NFO samples exhibited remarkable visible-light-driven catalytic CO2 reduction properties under mild reaction conditions with Ru(bpy)32+ sensitization. As the optimized sample, 16%-C/NFO achieved a 4-fold enhancement of CO production (17.49 µmol/h) compared with that of pure NFO. The C/NFO samples demonstrated good activity and structural stability in the CO2 photoreduction system. The carbon source of CO derived from CO2 was verified through isotopic labeling experiments using 13CO2. In situ photoluminescence and electrochemical characterizations confirmed the role of electron transfer intermediates of C/NFO. The synergistic effect of the nanosheet-like structure of NFO, combined with the surface functional groups of hydrochar, facilitated an exceptionally high rate of charge transfer and exposed abundant active adsorption sites for CO2, thereby promoting the efficient separation of photogenerated charge carriers and enhancing photocatalytic activity for CO2 reduction. This study presents a promising strategy for the rational design of hydrochar coupled with transition metal compound catalysts for efficient CO2 photoreduction.

Efficient and Selective Electrochemical Nitrate Reduction to N2 Using a Flow-Through Zero-Gap Electrochemical Reactor with a Reconstructed Cu(OH)2 Cathode: Insights into the Importance of Inter-Electrode Distance.

Electrochemically converting nitrate, a widely distributed nitrogen contaminant, into harmless N2 is a feasible and environmentally friendly route to close the anthropogenic nitrogen-based cycle. However, it is currently hindered by sluggish kinetics and low N2 selectivity, as well as scarce attention to reactor configuration. Here, we report a flow-through zero-gap electrochemical reactor that shows a high performance of nitrate reduction with 100% conversion and 80.36% selectivity of desired N2 in the chlorine-free system at 100 mg-N·L-1 NO3- while maintaining a rapid reduction kinetics of 0.07676 min-1. More importantly, the mass transport and current utilization efficiency are significantly improved by shortening the inter-electrode distance, especially in the zero-gap electrocatalytic system where the current efficiency reached 50.15% at 5 mA·cm-2. Detailed characterizations demonstrated that during the electroreduction process, partial Cu(OH)2 on the cathode surface was reconstructed into stable Cu/Cu2O as the active phase for efficient nitrate reduction. In situ characterizations revealed that the highly selective *NO to *N conversion and the N-N coupling step played crucial roles during the selective reduction of NO3- to N2 in the zero-gap electrochemical system. In addition, theoretical calculations demonstrated that improving the key intermediate *N coverage could effectively facilitate the N-N coupling step, thereby promoting N2 selectivity. Moreover, the environmental and economic benefits and long-term stability shown by the treatment of real nitrate-containing wastewater make our proposed electrocatalytic system more attractive for practical applications.

Construction of Core-shell Sb2 s3 @Cds Nanorod with Enhanced Heterointerface Interaction for Chromium-Containing Wastewater Treatment.

How to collaboratively reduce Cr(VI) and break Cr(III) complexes is a technical challenge to solve chromium-containing wastewater (CCW) pollution. Solar photovoltaic (SPV) technology based on semiconductor materials is a potential strategy to solve this issue. Sb2 S3 is a typical semiconductor material with total visible-light harvesting capacity, but its large-sized structure highly aggravates disordered photoexciton migration, accelerating the recombination kinetics and resulting low-efficient photon utilization. Herein, the uniform mesoporous CdS shell is in situ formed on the surface of Sb2 S3 nanorods (NRs) to construct the core-shell Sb2 S3 @CdS heterojunction with high BET surface area and excellent near-infrared light harvesting capacity via a surface cationic displacement strategy, and density functional theory thermodynamically explains the breaking of SbS bonds and formation of CdS bonds according to the bond energy calculation. The SbSCd bonding interaction and van der Waals force significantly enhance the stability and synergy of Sb2 S3 /CdS heterointerface throughout the entire surface of Sb2 S3 NRs, promoting the Sb2 S3 -to-CdS electron transfer due to the formation of built-in electric field. Therefore, the optimized Sb2 S3 @CdS catalyst achieves highly enhanced simulated sunlight-driven Cr(VI) reduction (0.154 min-1 ) and decomplexation of complexed Cr(III) in weakly acidic condition, resulting effective CCW treatment under co-action of photoexcited electrons and active radicals. This study provides a high-performance heterostructured catalyst for effective CCW treatment by SPV technology.

Modulating CoFeOX Nanosheets Towards Enhanced CO2 Photoreduction to Syngas: Effect of Calcination Temperature and Mixed-Valence Multi-Metals.

CoFeOX nanosheets were synthesized by a facile coprecipitation and calcination method. The effect of calcination temperature on the crystal texture, morphology and surface areas of CoFeOX were fully explored. CoFeOX sample calcined at 600 °C (CoFeOX -600) showed superior catalytic performance for the reduction of CO2 under visible light. Compared with the pure Ru(bpy)3 2+ -sensitized CO2 reduction system, the CoFeOX -added system achieved 19-fold enhancement of CO production (45.7 µmol/h). The mixed valence state and nanosheet-like structure of CoFeOX cocatalyst support its ultra-high charge transfer and abundant CO2 active adsorption sites exposure, which promote the separation of photogenerated charges, and thus improve the photocatalytic CO2 reduction activity. Carbon source of CO from CO2 was verified by 13 CO2 isotopic labelling experiment. Repeated activity experiments confirmed the good stability of CoFeOX in the CO2 photoreduction system. This work would provide prospective insights into developing novel cost-effective, efficient, and durable non-precious metal cocatalysts to improve the efficiency of photocatalytic reduction of CO2 .

Enhanced removal of Cr(III)-EDTA chelates from high-salinity water by ternary complex formation on DETA functionalized magnetic carbon-based adsorbents.

A novel amino-functionalized magnetic adsorbent (Fe3O4@C@DETA) was developed for adsorption of Cr(III) and Cr(III)-EDTA from wastewater. Fe3O4@C@DETA were successfully prepared by modification of Fe3O4@C with diethylenediamine (DETA), which exhibits a core-shell structure and sufficient saturation magnetization. Fe3O4@C@DETA exhibits much better adsorption performance for Cr(III) and its chelates than the Fe3O4@C because of newly introduced amino active sites. The enhanced adsorption capacity of Fe3O4@C@DETA for Cr(III) is 44.74 mg g-1 (at 25 °C and pH 3.0), which is due to the surface coordination with the newly introduced amino functional sites. The Cr(III)-EDTA anions as a whole was adsorbed through the electrostatic interaction with protonated amino species of the Fe3O4@C@DETA and have maximum adsorption capacity of 47.27 mg g-1 (at 25 °C and pH 3.0). The adsorption data of free and EDTA coordinated Cr(III) were followed the Langmuir equation, while the adsorption dynamics was well explained by pseudo second order model indicating the chemical nature of adsorption process. The higher concentration of Ca2+ ions in the wastewater compete for adsorption sites and inhibit the Cr(III) removal, while on other hand Ca2+ ions promotes the adsorption of Cr(III)-EDTA, because of electrostatic interaction with adsorbent active sits. Furthermore, the adsorbent can be easily separated by external magnetic field and regenerated in acidic solution. The adsorbent is stable, recyclable and have more than 75% regeneration efficiency and can be repeatedly used in the adsorption process.

Plasmonic Hot Electrons from Oxygen Vacancies for Infrared Light-Driven Catalytic CO2 Reduction on Bi2 O3-x.

Current plasmonic photocatalysts are mainly based on noble metal nanoparticles and rarely work in the infrared (IR) light range. Herein, cost-effective Bi2 O3-x with oxygen vacancies was formed in situ on commercial bismuth powder by calcination at 453.15 K in atmosphere. Interestingly, defects introduced into Bi2 O3-x simultaneously induced a localized surface plasmon resonance (LSPR) in the wavelength range of 600-1400 nm and enhanced the adsorption for CO2 molecules, which enabled efficient photocatalysis of CO2 -to-CO (ca. 100 % selectivity) even under low-intensity near-IR light irradiation. Significantly, the apparent quantum yield for CO evolution at 940 nm reached 0.113 %, which is approximately 4 times that found at 450 nm. We also showed that the unique LSPR allows for the realization of a nearly linear dependence of photocatalytic CO production rate on light intensity and operating temperature. Finally, based on an IR spectroscopy study, an oxygen-vacancy induced Mars-van Krevlen mechanism was proposed to understand the CO2 reduction reactions.

Removal of Mercury Ions from Aqueous Solutions by Crosslinked Chitosan-based Adsorbents: A Mini Review.

Abatement of mercury emissions in air and waters has become a global challenge due to the toxicity of mercury species for life, yet actual remediation techniques are limited. In particular, adsorption of mercury ions onto solids is widely used but most adsorption techniques are not specific, and in turn, removal efficiency is lower. Adsorbents developed so far include activated carbon, clay, bentonite, cellulose and chitosan. Chitosan derivatives have recently attracted research attention for water purification because their molecular frames contain a large amount of -NH2 and -OH groups that can chelate with metal ions specifically. This manuscript reviews recent advances in chitosan-based adsorbents designed to remove mercury ions from wastewater. Focus is placed on their design, synthesis, characterization, adsorption properties, adsorption mechanisms and applications.

Preparation of Cu/GO/Ti electrode by electrodeposition and its enhanced electrochemical reduction for aqueous nitrate.

A Cu/GO/Ti electrode was prepared by electrodeposition for removal of nitrate by means of the electrochemical reduction. The structure, morphology and characteristics of the electrode were characterized by scanning electron microscopy (SEM), Raman spectroscopy (RS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical workstation, and Cu/GO/Ti was used as the cathode to remove nitrate in water by electrochemical process. Characterization results indicated that GO was successfully deposited on the Ti plate and it was partially reduced to reduced graphene. Dendritic and granular Cu particles are agglomerated on the surface of GO layer by chemical interaction in the form of metallic Cu, Cu2O and CuO, and the dendrite Cu layer increased the specific surface area of Cu layer. The addition of GO layer increases the electroreduction activity for nitrate. Furthermore, through comparison with Cu/Ti electrode, Cu/GO/Ti electrode improved the percentage of nitrate removal from 78.8% to 91.5%, and energy consumption decreased from 0.82 to 0.47 kW h/g NO3--N. The present results showed the promising application of GO-based electrodes with Cu in electrocatalytic nitrate removal.

Active Site-Directed Tandem Catalysis on Single Platinum Nanoparticles for Efficient and Stable Oxidation of Formaldehyde at Room Temperature.

The application of tandem catalysis is rarely investigated in degrading organic pollutants in the environment. Herein, a tandem catalyst on single platinum (Pt) nanoparticles (Pt0 NPs) is prepared for the sequential degradation of formaldehyde (HCHO) to carbon dioxide gas [CO2(g)] at room temperature. The synthesis approach includes coating of uniform Pt NPs on SrBi2Ta2O9 platelets using a photoreduction process, followed by calcination of the sample in the atmosphere to tune partial transformation of Pt0 atoms to Pt2+ ions in the tandem catalyst. The conversion of HCHO to CO2(g) is monitored by in situ Fourier transform infrared spectroscopy, which shows first conversion of HCHO to CO32- ions onto Pt0 active sites and subsequently the conversion of CO32- ions to CO2(g) by neighboring Pt2+ species of the catalyst. The later process with Pt2+ species does not allow CO32- poisoning of the catalyst. The enhanced activity of the prepared tandem catalyst to oxidize HCHO is maintained continuously for 680 min. Comparatively, the catalyst without Pt2+ shows activity for only 40 min. Additionally, the tandem catalyst presented herein performs better than the Pt/titanium dioxide (TiO2) catalyst to degrade HCHO. Overall, the tandem catalyst may be applied to degrade organic pollutants efficiently.

Simultaneous band-gap narrowing and carrier-lifetime prolongation of organic-inorganic trihalide perovskites.

The organic-inorganic hybrid lead trihalide perovskites have been emerging as the most attractive photovoltaic materials. As regulated by Shockley-Queisser theory, a formidable materials science challenge for improvement to the next level requires further band-gap narrowing for broader absorption in solar spectrum, while retaining or even synergistically prolonging the carrier lifetime, a critical factor responsible for attaining the near-band-gap photovoltage. Herein, by applying controllable hydrostatic pressure, we have achieved unprecedented simultaneous enhancement in both band-gap narrowing and carrier-lifetime prolongation (up to 70% to ∼100% increase) under mild pressures at ∼0.3 GPa. The pressure-induced modulation on pure hybrid perovskites without introducing any adverse chemical or thermal effect clearly demonstrates the importance of band edges on the photon-electron interaction and maps a pioneering route toward a further increase in their photovoltaic performance.

Two-Dimensional Layered Zinc Silicate Nanosheets with Excellent Photocatalytic Performance for Organic Pollutant Degradation and CO2 Conversion.

Two-dimensional (2D) photocatalysts are highly attractive for their great potential in environmental remediation and energy conversion. Herein, we report a novel layered zinc silicate (LZS) photocatalyst synthesized by a liquid-phase epitaxial growth route using silica derived from vermiculite, a layered silicate clay mineral, as both the lattice-matched substrate and Si source. The epitaxial growth of LZS is limited in the 2D directions, thus generating the vermiculite-type crystal structure and ultrathin nanosheet morphology with thicknesses of 8-15 nm and a lateral size of about 200 nm. Experimental observations and DFT calculations indicated that LZS has a superior band alignment for the degradation of organic pollutants and reduction of CO2 to CO. The material exhibited efficient photocatalytic performance for 4-chlorophenol (4-CP) degradation and CO2 conversion into CO and is the first example of a claylike 2D photocatalyst with strong photooxidation and photoreduction capabilities.

Cooperative Effects of Zwitterionic-Ionic Surfactant Mixtures on the Interfacial Water Structure Revealed by Sum Frequency Generation Vibrational Spectroscopy.

Cooperative effects of a series of equimolar binary zwitterionic-ionic surfactant mixtures on the interfacial water structure at the air-water interfaces have been studied by sum frequency generation vibrational spectroscopy (SFG-VS). For zwitterionic surfactant palmityl sulfobetaine (SNC16), anionic surfactant sodium hexadecyl sulfate (SHS), and cationic surfactant cetyltrimethylammonium bromide (CTAB) with the same length of alkyl chain, significantly enhanced ordering of interfacial water molecules was observed for the zwitterionic-anionic surfactant mixtures SNC16-SHS, indicating that SNC16 interacts more strongly with SHS than with CTAB because of the strong headgroup-headgroup electrostatic attraction for SNC16-SHS. Meanwhile, the SFG amplitude ratio of methyl and methylene symmetric stretching modes was used to verify the stronger interaction between SNC16 and SHS. The conformational order indicator increased from 0.64 for SNC16 to 7.17 for SNC16-SHS but only 0.94 for SNC16-CTAB. In addition, another anionic surfactant sodium dodecyl sulfate (SDS) was introduced to study the influence of chain-chain interaction. Decreased SFG amplitude of interfacial water molecules for SNC16-SDS was observed. Therefore, both the headgroup-headgroup electrostatic interaction and chain-chain van der Waals attractive interaction of the surfactants play an important role in enhancing the ordering of interfacial water molecules. The results provided experimental and theoretical bases for practical applications of the surfactants.

Rapid mineralization of methyl orange by nanocrystalline-assembled mesoporous Cu2O microspheres.

In this study, nanocrystalline-assembled mesoporous Cu2O microspheres (MCMs) with enhanced visible-light driven photocatalytic activity were synthesized by a facile one-step hydrothermal method. MCMs exhibit excellent visible-light driven photocatalytic activity with 85% removal of methyl orange (MO) (60% removal of total organic carbon (TOC)) in 40 min. The excellent photocatalytic performance is dependent on the specific morphology and excellent visible-light absorption ability. Interestingly, MCMs can efficiently remove MO with or without light. The amount and categories of active species were determined by electron paramagnetic resonance and photoluminance (PL). Reactive oxygen species (ROS) (mainly ·[Formula: see text] and H2O2) and Cu (I) radicals are important in fading and further mineralization of MO. With the assistance of gas chromatography-mass spectrometer , TOC and x-ray photoelectron spectroscopy, the degradation pathways in light and dark conditions were analyzed. It has been proven that MO could be efficiently mineralized by ROS generated in light, while reaction in dark condition was more likely to be an efficient fading process.

Transformation of Polycyclic Aromatic Hydrocarbons and Formation of Environmentally Persistent Free Radicals on Modified Montmorillonite: The Role of Surface Metal Ions and Polycyclic Aromatic Hydrocarbon Molecular Properties.

This paper presents the transformation of PAHs (phenanthrene, anthracene, benzo[a]anthracene, pyrene, and benzo[a]pyrene) on montmorillonite clays that are modified by transition-metal ions [Fe(III), Cu(II), Ni(II), Co(II), or Zn(II)] at room temperature (∼23 °C). The decay of these PAHs follows first-order kinetics, and the dependence of the observed rate constants ( kobs, day-1) on the presence of metal ions follows the order Fe(III) > Cu(II) > Ni(II) > Co(II) > Zn(II). The values of kobs show reasonable linear relationships with the oxidation potentials of the PAHs and the redox potentials of the metal ions. Notably, transformation of these PAHs results in the formation of environmentally persistent free radicals (EPFRs), which are of major concern due to their adverse effects on human health. The potential energy surface (PES) calculations using density functional theory were performed to understand the trends in kobs and the plausible mechanisms for radical formation from the PAHs on modified clays. The yields and stability of these EPFRs from anthracene and benzo[a]pyrene on clay surfaces varies with both the parent PAH and the metal ion. The results demonstrated the potential role of metals in the formation and fate of PAH-induced EPFR at co-contaminated sites.

Environmentally Persistent Free Radicals in Soils of Past Coking Sites: Distribution and Stabilization.

This study presents the existence of environmentally persistent free radicals (EPFRs) in soils of past coking sites, mainly contaminated by polycyclic aromatic hydrocarbons (PAHs). Measurements of EPFRs were conducted by electron paramagnetic resonance (EPR) technique with numerous soil samples, which were collected from different distances (0-1000 m) and different depths (0-30 cm) of three contaminant sources. EPR signals with ∼3 × 1017 radicals/g of the soil samples were obtained, which are very similar to that generated in PAHs contaminated clays, that is, g = 2.0028-2.0036. Concentrations of PAHs and soil components were determined to understand their role in producing EPFRs. PAHs, clay, and iron predominately contributed to generating EPRFs. Meanwhile, organic matter negatively influenced the production of EPRFs. The effects of environmental factors (moisture and oxic/anoxic) were also studied to probe the persistency of EPFRs under various simulated conditions. The EPFRs are stable under relatively dry and oxic conditions. Under anoxic conditions without O2 and H2O, the spin densities decrease initially, followed by gradual increase before attaining constant values in two months period time. The present work implies that continuous formation of EPFRs induced by PAHs is largely responsible for the presence of relatively stable radicals in soils of coking sites.

Freestanding MoO2/Mo2C imbedded carbon fibers for Li-ion batteries.

Flexible and freestanding MoO2/Mo2C imbedded carbon fibers (MoO2/Mo2C ICFs) have been successfully synthesized via an integrated procedure including electrospinning, thermo-plastication in air and reduction/carbonization at high temperature. A series of techniques such as SEM, TEM, N2 adsorption-desorption analysis, XRD, TGA, IR and XPS have been employed to systemically characterize the MoO2/Mo2C ICFs. In particular, it is observed that the MoO2/Mo2C ICFs derived from phosphomolybdic acid have more highly porous structures than those derived from molybdic acid. Most impressively, the obtained MoO2/Mo2C ICFs are directly used as binder- and current collector-free anode materials for LIBs, which exhibit desirable rate capability and satisfactory cycling performance. The electrochemical investigations illustrated that the MoO2/Mo2C ICFs could deliver an initial discharging capacity of 1422.0 mA h g-1 with an original coulombic efficiency of 63.3%, and the subsequent reversible capacity could reach as high as 1103.6 mA h g-1 even after 70 cycles at a current density of 0.1 A g-1. Such a capacity is larger than the theoretical capacity of MoO2 (838 mA h g-1) and pure carbon fibers (460.5 mA h g-1). More importantly, the MoO2/Mo2C ICFs exhibited an excellent rate performance with a capacity of 445.4 mA h g-1 even at a charging current density of 1.6 A g-1. The remarkable enhancement in rate capability and long cycling performance resulted from a synergistic effect between the MoO2 nanoparticles and porous carbon fiber matrix. This methodology can be widely extended to fabricate other metal oxide/carbon composites for significant energy storage and conversion applications.

Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

Selective and sensitive CQD-based sensing platform for Cu2+ detection in Wilson's disease.

Excessive Cu2+ intake can cause neurological disorders (e.g. Wilson's disease) and adversely affect the gastrointestinal, liver, and kidney organs. The presence of Cu2+ is strongly linked to the emergence and progression of Wilson's disease (WD), and accurately measuring the amount of copper is a crucial step in diagnosing WD at an early stage in a clinical setting. In this work, CQDs were fabricated through a facile technique as a novel fluorescence-based sensing platform for detecting Cu(II) in aqueous solutions, and in the serum samples of healthy and affected individuals by WD. The CQDs interact with Cu(II) ions to produce Turn-on and Turn-off states at nano-molar and micro-molar levels, respectively, with LODs of 0.001 µM and 1 µM. In fact, the Cu2+ ions can act like a bridge between two CQDs by which the charge and electron transfer between the CQDs may increase, possibly can have significant effects on the spectroscopic features of the CQDs. To the best of our knowledge, this is the first reported research that can detect Cu(II) at low levels using two different complexation states, with promising results in testing serum. The potential of the sensor to detect Cu(II) was tested on serum samples from healthy and affected individuals by WD, and compared to results obtained by ICP-OES. Astonishingly, the results showed an excellent correlation between the measured Cu(II) levels using the proposed technique and ICP-OES, indicating the high potential of the fluorimetric CQD-based probe for Cu(II) detection. The accuracy, sensitivity, selectivity, high precision, accuracy, and applicability of the probe toward Cu(II) ions make it a potential diagnostic tool for Wilson's disease in a clinical setting.

Multisite Cocatalysis: Single atomic Pt2+/Pt0 active sites synergistically improve the simulated sunlight driven H2O-to-H2 conversion performance of Sb2S3 nanorods.

Single atomic metal (SAM) cocatalysis is a potential strategy to improve the performance of photocatalytic materials. However, the cocatalytic mechanism of SAM sites in different valence states is rarely reported. Herein, single atomic Pt2+/Pt0 active sites were anchored on Sb2S3 nanorods to synergistically improve the photoactivity for hydrogen production under simulated sunlight. Experimental results and density functional theory calculations indicated that the coexistence of single atomic Pt2+/Pt0 sites synergistically improves the broadband light harvesting and promotes the Sb2S3-to-Pt electron transfer following inhibited photoexciton recombination kinetics and enhanced H proton adsorption capacity, resulting higher and more durable photoactivity for hydrogen production. Therefore, the optimal Sb2S3-Pt0.9‰ composite catalyst achieved remarkably enhanced hydrogen evolution rate of 1.37 mmol∙g-1∙h-1 (about 105-fold greater of that of Sb2S3 NRs) under faintly alkaline condition, and about 5.41 % of apparent quantum yield (AQY700 nm) was achieved, which shows obvious superiority in hydrogen production by contrasting with the reported Sb2S3-based photocatalysts and conventional semiconductor photocatalytic materials modified with noble metals. This study elucidate a well-defined mechanism of multisite cocatalysis for photoactivity improvement.

Coal fly ash and bottom ash low-cost feedstocks for CO2 reduction using the adsorption and catalysis processes.

Combustion of fossil fuels, industry and agriculture sectors are considered as the largest emitters of carbon dioxide. In fact, the emission of CO2 greenhouse gas has been considerably intensified during the last two decades, resulting in global warming and inducing variety of adverse health effects on human and environment. Calling for effective and green feedstocks to remove CO2, low-cost materials such as coal ashes "wastes-to-materials", have been considered among the interesting candidates of CO2 capture technologies. On the other hand, several techniques employing coal ashes as inorganic supports (e.g., catalytic reduction, photocatalysis, gas conversion, ceramic filter, gas scrubbing, adsorption, etc.) have been widely applied to reduce CO2. These processes are among the most efficient solutions utilized by industrialists and scientists to produce clean energy from CO2 and limit its continuous emission into the atmosphere. Herein, we review the recent trends and advancements in the applications of coal ashes including coal fly ash and bottom ash as low-cost wastes to reduce CO2 concentration through adsorption and catalysis processes. The chemical routes of structural modification and characterization of coal ash-based feedstocks are discussed in details. The adsorption and catalytic performance of the coal ashes derivatives towards CO2 selective reduction to CH4 are also described. The main objective of this review is to highlight the excellent capacity of coal fly ash and bottom ash to capture and selective conversion of CO2 to methane, with the aim of minimizing coal ashes disposal and their storage costs. From a practical view of point, the needs of developing new advanced technologies and recycling strategies might be urgent in the near future to efficient make use of coal ashes as new cleaner materials for CO2 remediation purposes, which favourably affects the rate of global warming.