Intermediate Absorption Research Articles

Regulating the electronic structure of Ni3Se4-MoSe2 by coupling with ZIF-derived Co@C promotes boosted urea-assisted water splitting at industrial current density

Adopting urea oxidation reaction (UOR) as an alternative to oxygen evolution reaction (OER) is a prospective approach to achieve energy-saving H2 generation as well as purify wastewater with abundant urea, while the industrial application of bifunctional catalysts for hydrogen evolution reaction (HER) and UOR still remains challenge. Herein, novel coleslaw-like arrays Ni3Se4-MoSe2/Co@C electrocatalyst is fabricated by coupling Ni3Se4-MoSe2 heterointerface with Co-ZIF derived Co@C, in which the synergistic effects of Ni3Se4-MoSe2 and Co@C can tailor the electronic state caused by Ni, Mo, Se and Co atoms, contributing to the modulated d-band center and charge redistribution, hence balancing the absorption and desorption of HER and UOR reaction intermediates and realizing facilitated HER and UOR activities. Furthermore, the coleslaw-like arrays could expose more active sites as well as speed up mass transport. As a result, Ni3Se4-MoSe2/Co@C shows ultralow potentials of 189 mV and 1.427 V to achieve industrial current density of 1000 mA·cm−2 with small Tafel slopes of 56.5 and 30.2 mV·dec-1 towards HER and UOR with exceptional long durability, respectively. Impressively, a remarkably decreased cell voltage of 1.98 V is seen to achieve 1000 mA·cm−2 for urea-assisted water splitting. This study introduces a new strategy to producing non-noble-based selenides with ZIF derivative to realize bifunctional application in energy-saving H2 production with industrial treatment of urea wastewater.

Enhanced catalytic performance and antichlorine poisoning over Cu-doped cobalt oxide nanosheets for chlorobenzene oxidation

The degradation of Chlorinated volatile organic compounds (CVOCs) by catalytic oxidation forms toxic products, and catalysts may be poisoned by chlorine at low temperatures. To address this, a Cu-assisted strategy is proposed for enhancing the catalytic degradation of chlorobenzene (CB) over cobalt oxide nanosheets. The Cu-doped Co3O4 catalysts exhibited lower T90 values (temperatures with 90 % conversion) and improved stability compared to the unmodified catalyst. These results were attributed to strong metal-metal interactions between Cu species and cobalt oxide nanosheets, which showed a high specific surface area, reduced binding energy of lattice oxygen, higher surface oxygen concentration, and more surface Co3+ species. These properties promoted low-temperature catalytic activity. In addition, the disappearance of Cu2+ satellite peak after the catalyst is used, indicating that the Cu2+ also contributes to the catalytic activity. Furthermore, the in situ FTIR spectra provided details about the reaction mechanism of CB degradation over Cu-doped cobalt oxide nanosheets. The oxygen vacancy generation and the surface absorption of chlorine-containing intermediates were calculated using density functional theory calculations. This study provides new insight into novel pathways for catalyst design aimed at CB degradation.

Impact of copper on activity, selectivity, and deactivation in the photocatalytic reduction of CO2 over TiO2

The photocatalytic reduction of CO2 to hydrocarbons may be a promising mechanistic route to reduce greenhouse gas CO2, convert it into useful products, and limit the direct emission of CO2. The photocatalytic reduction of CO2 is a reaction in which photons activate the photocatalyst by generating reduced and oxidized sites, that are re-oxidized and re-reduced by the reactants. The photocatalytic reduction of CO2 can produce various products, including CO, formic acid, formaldehyde, methanol, methane, etc.Here, the activity/selectivity of produced hydrocarbons in the presence of oxygen on various photocatalysts (TiO2, 5 wt%Cu-TiO2, 5 wt%Cu-C-TiO2) was determined.The reaction rate increased with increasing reaction time up to the first half an hour of the reaction but then started to decrease with photocatalysts, indicating photocatalyst deactivation, a rate-limiting step by hydroxyl radicals and adsorption of intermediates on TiO2. Carbon deposition as the origin of photocatalyst deactivation was confirmed using the TGA of the spent photocatalyst. Additionally, absorption of intermediates on spent catalysts were confirmed by FTIR. On the other hand, the conversion increased with time when copper was used as a promoter on a TiO2 compared with TiO2 due to its larger surface area and having more active sites.The photocatalysts were characterized using BET, ICP-OES, XRD, TGA, XPS, Fourier-Transform Infrared Spectroscopy (FTIR), and UV–Vis. The focus of this study was to determine the activity and efficacy of different photocatalysts (TiO2, 5 wt%Cu-TiO2, 5 wt%Cu-C-TiO2) by gas phase measurement, with a particular emphasis on obtaining reproducible data on conversion and selectivity as a function of irradiation time.The copper on TiO2 was found to be more selective towards sodium formate/formic acid with a maximum selectivity of ∼90 % in 4 h and had higher activity (74.3 µmol gcat-1 h-1). A maximum CO with a selectivity of 86 % was found when TiO2 was used in 4 h.Copper transfer electrons on the TiO2 surface enhance CO2 adsorption on the catalytic surface and is the reason for having higher valuable product on Cu-C-TiO2 and Cu-TiO2 compared with TiO2. Carbon in this experiment did not have a role and its effect was negligible.

Utilization of waste marble dust as cement and sand replacement in concrete

In this paper, CaCO3 waste marble dust (WMD) has been utilized in the production of concrete. Raw materials (Cement, Sand, WMD and Crush) were collected from Peshawar, Khyber Pakhtunkhwa, Pakistan. Concrete cubes were molded in the laboratory and investigated by XRD. Effect of WMD addition to the concrete was studied. It was reported that 10% addition of WMD as cement replacement showed enhanced performance of the compressive strength as compared to sand replaced WMD blended concrete. Increment in WMD contents beyond 10% resulted in significant decrement of compressive strength. Substituting WMD with cement resulted in a decrement of 29.76%, while with sand, the decrement was 6.09%. Concrete made with cement replaced WMD showed the lowest water absorption rate over 7 days curing as compared to sand replaced (intermediate water absorption) and clean concrete (highest water absorption) samples.Graphical

Preferential heteroatom substitution into ZnIn2S4 nanosheets boosts photocatalytic hydrogen production

Interior modification through preferential substitution of heteroatoms in 2D materials can rescue surface reactive sites for enhanced charge kinetics and photo-activity. Here, Ru and Ni heteroatoms were successfully incorporated in ZnIn2S4 (ZIS) nanosheets via a simple hydrothermal technique. Ru-ZIS photocatalysts exhibited improved photo–water splitting activity (26,400 µmol. h−1g−1) and good stability than that of Ni-ZIS and pristine ZIS under simulated sunlight, which may be related to the increase in reactive sites with Ru substitution, optimized adsorption-free energy of the reaction intermediates and charge kinetics. Ru substitution influenced Zn site availability and thus coordinated bonding with surrounding S ions. Ru-ZIS showed excellent hydrogen evolution performance and minimal change in Gibbs free energy (ΔGH, ∼0 eV). By analyzing the density of states, both Ru and S sites had greater H* intermediate absorption abilities. This study elaborates on the effect of preferential heteroatom substitution on photocatalytic performance and has widespread applications.

Single-atom Fe catalysts with pyrrolic-type FeN4 sites for efficient oxygen reduction reaction: Identifying the roles of different N species

Developing electrocatalysts with efficient cathode oxygen reduction reaction (ORR), for example, iron-based single-atom catalysts (Fe-SACs), has been deemed necessary to accelerate the commercialisation process of zinc (Zn)–air batteries. Nevertheless, determining how various nitrogen species and active metal centres coordinate on an atomic scale remains unclear and inadequately explained. Herein, we demonstrate a soft-template-aided technique using Fe-containing molecules (e.g. iron phthalocyanine [FePc], Fe-1,10-phenanthroline [Fe-Phen] and Fe-glucose) to enhance the performance of Fe-SACs in terms of ORR. In this technique, FePc molecules can be converted into atomically dispersed pyrrolic-type iron–nitrogen (FeN4) sites during a pyrolytic process. The resultant catalyst exhibits excellent ORR activity (half-wave potential = 0.90 V) in alkaline medium and standing battery performance when used in Zn–air batteries (peak power density = 197.3 mW cm−2 and specific capacity = 796.2 mAh g−1). As per the findings from control experiments and characterisation studies, electron transfer between the support and the active Fe centre amplifies the ORR performance. Theoretical calculations substantiate that Fe sites coordinated with pyrrolic N atoms govern the electronic configuration of the catalysis, reducing the free energy absorption of reaction intermediates and thus increasing its intrinsic ORR capability. Herein, we aim to offer a fresh perspective on the relation between coordination environments and catalytic activity in ORR catalysts.

Phenylacetylene-Terminated Poly(Ethylene Glycol) as Ligands for Colloidal Noble Metal Nanoparticles: a New Tool for "Grafting to" Approach.

We report a new design of polymer phenylacetylene (PA) ligands and the ligand exchange methodology for colloidal noble metal nanoparticles (NPs). PA-terminated poly(ethylene glycol) (PEG) can bind to metal NPs through acetylide (M-C≡C-R) that affords a high grafting density. The ligand-metal interaction can be switched between σ bonding and extended π backbonding by changing grafting conditions. The σ bonding of PEG-PA with NPs is strong and it can compete with other capping ligands including thiols, while the π backbonding is much weaker. The σ bonding is also demonstrated to improve the catalytic performance of Pd for ethanol oxidation and prevent surface absorption of the reaction intermediates. Those unique binding characteristics will enrich the toolbox in the control of colloidal surface chemistry and their applications using polymer ligands.

Photoaquation of cis-[Rh(dppz)(phen)Cl2]Cl complex prospective as potential light-activated anti-cancer agent

The photoactivated drug usage in anti-cancer therapy, the working mechanism of which doesn’t rely on the formation of reactive oxygen species, allows reducing damage to healthy tissue by controlling toxicity. For instance, light-activated Rh(III) complexes show nuclease activity after irradiation with UV and visible light. However, literature analysis shows a lack of descriptions of basic photochemical mechanisms. Here we report the study of cis-[Rh(dppz)(phen)Cl2]Cl (DPPZPHEN, dppz is dipyrido[3,2-a:2′,3′-c]phenazine, phen is 1,10-phenanthroline) photochemistry in water solutions using stationary photolysis, nanosecond laser flash photolysis and ultrafast pump–probe spectroscopy. After the irradiation with 308 nm light, DPPZPHEN undergoes aquation, which results in the substitution of one chloride ligand by a water molecule and leads to the formation of [Rh(dppz)(phen)(H2O)Cl]Cl2. UV–vis spectra of complex and capillary electrophoresis data were collected and discussed. Laser flash photolysis (355 nm) demonstrates intermediate absorption attributed to the lowest electronic excited state (triplet) of the initial complex. The study of primary photophysical processes showed a rather complicated behavior of transient absorption, which could be described by a set of four exponential functions. The early photophysical processes were described by the scheme including the formation of two excited states of different natures, namely a dppz-based IL state and an LMCT state.

Orbital Occupancy Modulation to Optimize Intermediate Absorption for Efficient Electrocatalysts in Water Electrolysis and Zinc-Ethanol-Air Battery.

Spin engineering is a promising way to modulate the interaction between the metal d-orbital and the intermediates and thus enhance the catalytic kinetics. Herein, an innovative strategy is reported to modulate the spin state of Co by regulating its coordinating environment. o-c-CoSe2 -Ni is prepared as pre-catalyst, then in situ electrochemical impedance spectroscopy (EIS)and in situ Raman spectroscopy are employed to prove phase transition, and CoOOH/Co3 O4 is formed on the surface as active sites. In hybrid water electrolysis, the voltage has a negative shift, and in zinc-ethanol-air battery, the charging voltage is lowered and the cycling stability is greatly increased. Coordinated atom substitution and crystalline symmetry change are combined to regulate the absorption ability of reaction intermediates with balanced optimal adsorption. Coordinated atom substitution weakens the adsorption while the crystalline symmetry change strengthens the adsorption. Importantly, the tetrahedral sites are introduced by Ni doping which enables the co-existence of four-coordinated sites and six-coordination sites in o-c-CoSe2 -Ni. The dz2 + dx2 -y2 orbital occupancy decreases after the atomic substitution, while increases after replacing the CoSe6 -Oh field with CoSe6 -Oh /CoSe4 -Td . This work explores a new direction for the preparation of efficient catalysts for water electrolysis and innovative zinc-ethanol-air battery.

Janus Zn-IV-VI: Robust Photocatalysts with Enhanced Built-In Electric Fields and Strain-Regulation Capability for Water Splitting.

The use of 2D materials to produce hydrogen (H2 ) fuel via photocatalytic water splitting has been intensively studied. However, the simultaneous fulfillment of the three essential requirements-high photon utilization, rapid carrier transfer, and low-barrier redox reactions-for wide-pH-range production of H2 still poses a significant challenge with noadditional modulation. By employing the first-principles calculations, it has been observed that the Janus ZnXY2 structures (X = Si/Ge/Sn, Y = S/Se/Te) exhibit significantly enhanced built-in electric fields (0.20-0.36eVÅ-1 ), which address the limitations intrinsically. Compared to conventional Janus membranes, the ductile ZnSnSe2 and ZnSnTe2 monolayers have stronger regulation of electric fields, resulting in improved electron mobility and excitonic nature (Ebinding = 0.50/0.35eV). Both monolayers exhibit lower energy barriers of hydrogen evolution reaction (HER, 0.98/0.86eV, pH = 7) and resistance to photocorrosion across pH 0-7. Furthermore, the 1% tensile strain can further boost visible light utilization and intermediate absorption. The optimal AC-type bilayer stacking configuration is conducive to enhancing electric fields for photocatalysis. Overall, Janus ZnXY2 membranes overcome the major challenges faced by conventional 2D photocatalysts via intrinsic polarization and external amelioration, enabling efficient and controllable photocatalysis without the need for doping or heterojunctions.

Ru doping induced interface engineering in flower-liked CoMoO4-RuO2 boosts oxygen electrocatalysis for rechargeable Zn-air battery

Constructing heterogeneous catalysts can significantly boost the electrocatalytic activity due to the improved intrinsic catalytic activity induced by tailored electronic structure and optimized chemisorption to the reaction intermediates. RuO2 based electrocatalysts are especially attractive due to the high catalytic activity of RuO2. To reduce the usage of noble metal and improve the catalytic activity of catalyst, CoMoO4-RuO2 micro-flower was synthesized using a facile hydrothermal-calcination method in this work. CoMoO4-RuO2 exhibits a low overpotential of 177 mV at 10 mA cm−2 for oxygen evolution reaction (OER) and a high half-wave potential of 0.858 V for oxygen reduction reaction (ORR). Moreover, the Zn-air battery assembled using CoMoO4-RuO2 exhibit shows a high maximum discharge power density of 149 mW cm−2 and a large open circuit voltage of 1.38 V. The good performance can be attributed to the incorporation of RuO2, which not only induces extra catalytic active sites, but also forms heterojunction with CoMoO4 to optimize the electronic structure of CoMoO4-RuO2, thereby achieving a better equilibrium of absorption and desorption of intermediates. The work provides insights into designing RuO2 based electrocatalysts for advanced electrocatalysis.

Cerium oxide boosted CoFe-N codoped carbon nanotubes with abundant oxygen-vacancies toward efficient oxygen reduction and methanol oxidation reaction

In this study, we designed a novel strategy that utilizes N-doped carbon nanotubes as the chemical bond supporter to stabilize ultrafine CoFe alloy and introduces secondary CeO2 active sites into the hybrid, resulting in the formation of CeO2/CoFe-NCNTs heterostructures with exceptional bifunctional electrocatalytic capabilities. To be specific, solution dispersion and high-temperature calcination methods were employed to create the CoFe-NCNTs active sites through the introduction of ethylenediamine into the network interstitials of Co-EDTA and Fe-EDTA. The CeO2/CoFe-NCNTs hybrid not only promotes oxygen absorption and conversion of intermediates, but also accelerates charge transfer capability, thus enhancing oxygen reduction reaction (ORR) performance, while simultaneously inducing boosted the methanol oxidation reaction (MOR) activity. Moreover, the well-dispersed CoFe nanoparticles within the hybrid hold significant potential for establishing metal-nitrogen bonds with the N-doped carbon nanotube network, resulting in efficient catalytic behavior driven by synergistic effects with CeO2 nanoparticles, which contributes to reactant activation. As expected, the resultant CeO2/CoFe-NCNTs-2 exhibits remarkable electrocatalytic performance, with a current density of 281.40 mA cm−2 at a scan rate of 200 mV s−1 and a low Tafel slope (71.3 mV dec−1) for MOR, as well as achieving excellent half-wave potential and onset potential values of 0.834 and 0.90 V (vs. RHE) for ORR. Additionally, it exhibits durable cycle stability for both MOR and ORR, retaining 92.8% and 96.4% of its initial current density during the I-t test, respectively. This work establishes a highly efficient bifunctional earth-abundant electrocatalysts for both anode and cathode reactions in methanol fuel cells.

Ultrafine PtMo Nanocrystals Confined on N‐Doped Carbon Toward Efficient pH‐Universal Hydrogen Evolution Reaction

AbstractPt‐based nanocrystals with tunable electronic structure and optimized atom efficiency are essential for boosting the hydrogen evolution reaction (HER) performance and further industrial application. However, the synthesis of uniform and ordered nanocrystals is still a challenge due to the uncontrollable size growth of metal particles, restricting the active sites toward the desired catalytic activity. Herein, the synthesis of ultrafine bimetal PtMo nanocrystals on N‐doped carbon (PtMo‐NC) through an anchoring‐sites engineering strategy is reported, in which the N‐rich carbon can provide abundant sites to anchor the metal atoms and suppress the over aggregation. The PtMo‐NC catalyst exhibits superior HER performance in both alkaline and acidic conditions, delivering a smaller overpotential (80 mV and 63 mV) at a current density of 100 mA cm−2 in alkaline and acidic media. Theoretical calculations reveal that the introduction of Mo atom into Pt can reduce the energy barrier of water molecule dissociation and optimize the H intermediate absorption strength on Pt sites, thus boosting the catalytic HER performance. This study offers a universal strategy to design ultrafine nanocatalysts to achieve high‐efficiency electrocatalysis.

Hydrogen and oxygen recombination reaction on Pt–Ni and Pt–Co based alloys using density functional theory

Density functional theory (DFT) calculations were used to investigate the surface performance of Pt, Ni, Co, and PtxTM1-x (0 ≤ x ≤ 1) alloys, as well as reaction intermediates (O, H, OH, OH + H, H2O) on these surfaces for H2/O2 recombination. The activity of the PtxTM1-x alloys towards H2/O2 recombination reaction was probed using adsorption energies and reaction energies. The Pt3Co, Pt3Ni and PtNi3 alloys were found to be stable along the (111) miller index, with strong surface adsorption occurring on the PtNi3 (111) surface and weaker adsorption on the Pt3Co (111) surface. Enhanced reactivity was observed on the Pt3Ni and Pt3Co (111) surfaces for the (O* + H* → OH*) reaction step, while the Pt (111) surface was most suited for the (OH* + H* → H2O) reaction step. The OH* formation reaction step was inhibited on the PtNi3 (111) surface due to the strong surface absorption of the reaction intermediates. Overall, these results suggest that the Pt3Co (111) surface is a promising alternative catalyst for H2/O2 recombination compared to pristine Pt due to its performance in the O + H adsorption and OH* formation steps.

In situ catalytic cells for x-ray absorption spectroscopy measurement.

In catalysis, determining the relationship between the dynamic electronic and atomic structure of the catalysts and the catalytic performance under actual reaction conditions is essential to gain a deeper understanding of the reaction mechanism since the structure evolution induced by the absorption of reactants and intermediates affects the reaction activity. Hard x-ray spectroscopy methods are considered powerful and indispensable tools for the accurate identification of local structural changes, for which the development of suitable in situ reaction cells is required. However, the rational design and development of spectroscopic cells is challenging because a balance between real rigorous reaction conditions and a good signal-to-noise ratio must be reached. Here, we summarize the in situ cells currently used in the monitoring of thermocatalysis, photocatalysis, and electrocatalysis processes, focusing especially on the cells utilized in the BL14W1-x-ray absorption fine structure beamline at the Shanghai Synchrotron Radiation Facility, and highlight recent endeavors on the acquisition of improved spectra under real reaction conditions. This review provides a full overview of the design of in situ cells, aiming to guide the further development of portable and promising cells. Finally, perspectives and crucial factors regarding in situ cells under industrial operating conditions are proposed.

Graphene Twistronics: Tuning the Absorption Spectrum and Achieving Metamaterial Properties

Graphene twistronics using multilayer graphene is presented in such a way that it provides a metamaterial effect. This manuscript also analyzes the prediction of behavior using machine learning. The metamaterial effect is achieved by twisting the graphene layers. Graphene twistronics is a new concept for changing the electrical and optical properties of bilayer graphene by applying a small angle twist between the layers. The angle twists of 5°, 10°, and 15° are analyzed for the proposed graphene twistronics design. Tuning in the absorption spectrum is achieved by applying small twists to the angles of the bilayer graphene. Results in the form of absorption, conductivity, permeability, permittivity, and impedance are presented for different twist angles. The twisted graphene layers also demonstrate negative permittivity and negative permeability, similar to metamaterials. These negative refraction properties of graphene twistronics provide flexibility and transparency, which can be applied in photovoltaic applications. Machine-learning-based regression models are used to reduce the simulation time and resources. The results show that a regression model can reliably estimate intermediate wavelength absorption values with an R2 of 0.9999.

Temperature versus type: Which is the determining factor in biomass-based electrocatalyst performance?

Having high natural abundance enables biomass to be deliberately employed to prepare electrocatalysts by annealing processing. The great diversity of biomass originating from different types or parts is leading to concerns about consistency of product performance. Taking acidic and alkaline electroreduction of dioxygen as the object of study, we have demonstrated that processing temperatures exert much more powerful influence over structures and activities of biomass-based electrocatalysts than which parts of biomass are used. It has been found that initial discrepancies due to different parts are narrowed and aggregated by arithmetic means in terms of structures and activities at the same elevated temperatures, whereas there are wide gaps between electrocatalysts prepared at different processing temperatures even though they stem from the same part of biomass. We have also explored systematically how processing temperatures tailor pore width distributions and nitrogen species distributions and how these parameters tune mass transport and reaction intermediate absorption strengths with concomitant performance on the basis of a great deal of experimental and theoretical evidence. Hence, this work helps to address growing concerns about consistency of biomass-based electrocatalysts and to indicate the feasibility of their large-scale manufactures because temperature is the determining factor, not type.

Global Kinetics and Spectral Modeling of p-Methoxyphenyl Azide Photooxidation.

The kinetics of photooxidation of para-methoxyphenyl azide 1 was studied by flash photolysis with spectrophotometric detection of the absorption of active intermediates in an aerated acetonitrile solution at 295 K. The holistic set of experimental data including the consumption of cis-trans isomers of para-methoxyphenyl nitroso oxide 2 and the accumulation of photooxidation products (2Z,4E)-4-methoxy-6-oxo-hexa-2,4-diene-nitrile oxide 3 and bis-p-methoxy-azobenzene 4 monitored via the changes in the optical density of the solution in the wavelength range of 300-500 nm was treated to obtain the most complete information about the system under study. Flash photolysis of 1 results in the formation of the corresponding triplet nitrene, which either recombines to azobenzene 4 with a rate constant 2k4 = (8.7 ± 1.0) × 108 L/(mol s), or adds molecular oxygen to produce cis-trans isomers of nitroso oxide 2 with a total rate constant k5 = (1.0 ± 0.1) × 106 L/(mol s). The latter reaction is the main channel for nitrene consumption: the yield of 2 per consumed nitrene was found to be 90% higher at the cis/trans isomers ratio of 0.94 ± 0.04. The trans-isomer of 2 is chemically inert under the experimental conditions and is consumed in the trans-cis conformational transformation with the rate constant k6 = 0.45 c-1. The cis-isomer is thermodynamically more stable, k-6 = 0.16 c-1, but it is consumed irreversibly in the ortho-cyclization reaction with the rate constant k7 = 12.5 c-1. The final product, nitrile oxide 3, has intense absorption in the near UV region, λmax = 300 nm and εmax = 2 × 104 L/(mol·cm). This made it possible to determine the spectral characteristics of 2 isomers using nonlinear regression analysis. It was found λmax = 421 nm, εmax = (1.23 ± 0.07) × 104 L/(mol·cm), and δ = 1640 ± 10 cm-1 (half width at half maximum) for cis-2 and λmax = 462 nm, εmax = (1.57 ± 0.03) × 104 L/(mol·cm), and δ = 2150 ± 10 cm-1 for trans-2. The obtained spectral parameters are in good agreement with the results of optical spectra modeling for 2 isomers performed in the CIS(D,Full)/aug-cc-PVTZ//CASSCF(14,13)/ma-def2-TZVPP approximation: the calc-exp deviation for the absorption maximum was 0.05 eV (cis) and 0.12 eV (trans), the oscillator strengths were calculated to be 0.59 and 0.65, respectively.

Human-induced pollution and toxicity of river sediment by potentially toxic elements (PTEs) and accumulation in a paddy soil-rice system: A comprehensive watershed-scale assessment

This study aimed to assess pollution by potentially toxic elements (PTEs) in the Zarjoub and Goharroud river basins in northern Iran. Due to exposure to various types of pollution sources, these rivers are two of the most polluted rivers in Iran. They also play an important role in irrigation of paddy fields in the study area, increasing concerns about the contamination of rice grains by PTEs. Hence, we analyzed the concentrations of eight PTEs (i.e., As, Co, Cr, Cu, Mn, Ni, Pb, and Zn) at ten channel bed sediment sampling sites in each river, fifteen samples of paddy soils and fifteen co-located rice samples in the relevant watersheds. Results of the index-based assessment indicate moderate to heavy pollution and moderate toxicity for sediments in the Goharroud River, while both pollution and toxicity of the Zarjoub River sediment were characterized as moderate. Paddy soils in the watersheds were found to be moderate to heavily polluted by PTEs, but the values of the rice bioconcentration factor (RBCF) indicated intermediate absorption for Cu, Zn, and Mn, and weak and very weak absorption for Pb/Ni and As/Co/Cr, respectively. The concentration of Zn, Cu, Pb, and Cr was negatively correlated to the corresponding values of RBCF, highlighting the ability of rice grains to control bioaccumulation and regulate concentrations. Industrial/agricultural effluents, municipal wastewater, leachate of solid waste, traffic-related pollution, and weathering of parent materials were found to be responsible for pollution of the Zarjoub and Goharroud watersheds by PTEs. Mn, Cu, and Pb in rice grains might be responsible for non-carcinogenic diseases. Although weak absorption was observed for As and Cr in rice grains, the concentrations of these elements in rice grains indicate a high level of cancer risk if ingested. This study provides insights to control the pollution of sediment, paddy soils, and rice.

Synergistic Hybrid Electrocatalysts of Platinum Alloy and Single-Atom Platinum for an Efficient and Durable Oxygen Reduction Reaction.

Pt single-atom materials possess an ideal atom economy but suffer from limited intrinsic activity and side reaction of producing H2O2 in catalyzing the oxygen reduction reaction (ORR); platinum alloys have higher intrinsic activity but weak stability. Here, we demonstrate that anchoring platinum alloys on single-atom Pt-decorated carbon (Pt-SAC) surmounts their inherent deficiencies, thereby enabling a complete four-electron ORR pathway catalysis with high efficiency and durability. Pt3Co@Pt-SAC demonstrates an exceptional mass and specific activities 1 order of magnitude higher than those of commercial Pt/C. They are durable throughout 50000 cycles, showing only a 10 mV decay in half-wave potential. An in situ Raman analysis and theoretical calculations reveal that Pt3Co core nanocrystals modulate electron structures of the adjacent Pt single atoms to facilitate the intermediate absorption for fast kinetics. The superior durability is attributed to the shielding effect of the Pt-SAC coating, which significantly mitigates the dissolution of Pt3Co cores. The hybridizing strategy might promote the development of highly active and durable ORR catalysts.