Iron Carbides: Control Synthesis and Catalytic Applications in COx Hydrogenation and Electrochemical HER.

Catalytic transformation of COx (x = 1, 2) with renewable H2 into valuable fuels and chemicals provides practical processes to mitigate the worldwide energy crisis. Fe-based catalytic materials are widely used for those reactions due to their abundance and low cost. Novel iron carbides are particularly promising catalytic materials among the reported ferrous catalysts. Recently, a series of strategies has been developed for the preparation of iron carbide nanoparticles and their nanocomposites. Control synthesis of FeCx -based nanomaterials and their catalytic applications in COx hydrogenation and electrochemical hydrogen evolution reaction (HER) are reviewed. The discussion is focused on the unique catalytic activities of iron carbides in COx hydrogenation and HER and the correlation between structure and catalytic performance. Future synthesis and potential catalytic applications of iron carbides are also summarized.

Graphene-supported nanoscale zero-valent iron: removal of phosphorus from aqueous solution and mechanistic study.

Excess phosphorus from non-point pollution sources is one of the key factors causing eutrophication in many lakes in China, so finding a cost-effective method to remove phosphorus from non-point pollution sources is very important for the health of the aqueous environment. Graphene was selected to support nanoscale zero-valent iron (nZVI) for phosphorus removal from synthetic rainwater runoff in this article. Compared with nZVI supported on other porous materials, graphene-supported nZVI (G-nZVI) could remove phosphorus more efficiently. The amount of nZVI in G-nZVI was an important factor in the removal of phosphorus by G-nZVI, and G-nZVI with 20 wt.% nZVI (20% G-nZVI) could remove phosphorus most efficiently. The nZVI was very stable and could disperse very well on graphene, as characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS), Fourier Transform infrared spectroscopy (FT-IR) and Raman spectroscopy were used to elucidate the reaction process, and the results indicated that Fe-O-P was formed after phosphorus was adsorbed by G-nZVI. The results obtained from X-ray diffraction (XRD) indicated that the reaction product between nZVI supported on graphene and phosphorus was Fe3(PO4)2·8H2O (Vivianite). It was confirmed that the specific reaction mechanism for the removal of phosphorus with nZVI or G-nZVI was mainly due to chemical reaction between nZVI and phosphorus.

A sensitive flow injection chemiluminescence method for the determination of progesterone.

A sensitive flow injection (FI) chemiluminescence (CL) method was developed for the determination of trace amounts of progesterone. This method was based on the luminescent properties of the tris(1,10-phenanthroline) ruthenium(II) - potassium permanganate (KMnO4 ) - progesterone in acidic medium sensitized by Na2 SO3 . With the peak height as a quantitative parameter applying optimum conditions, the relative CL intensity was linear with progesterone concentration in the range of 1.0 × 10(-10) ∼ 6.0 × 10(-9) g·ml(-1) and 6.0 × 10(-9) ∼ 4.0 × 10(-8) g·ml(-1) with a detection limit of 7.1 × 10(-11) g·ml(-1) . The relative standard deviation (RSD) was 2.79% for 1.0 × 10(-8) g·ml(-1) progesterone (n = 11). The proposed method held low detection limit and was successfully applied to determination of progesterone in pharmaceutical preparations. The possible CL reaction mechanism was also discussed.

Flow-injection chemiluminescent determination of estrogen benzoate using the tris(1,10-phenanthroline) ruthenium(II)-permanganate system.

Chemiluminescence (CL) detection for the determination of estrogen benzoate, using the reaction of tris(1,10-phenanthroline)ruthenium(II)-Na(2)SO(3)-permanganate, is described. This method is based on the CL reaction of estrogen benzoate (EB) with acidic potassium permanganate and tris(1,10-phenanthroline)ruthenium(II). The CL intensity is greatly enhanced when Na(2)SO(3) is added. After optimization of the different experimental parameters, a calibration graph for estrogen benzoate is linear in the range 0.05-10 µg/mL. The 3 s limit of detection is 0.024 µg/mL and the relative standard deviation was 1.3% for 1.0 µg/mL estrogen benzoate (n = 11). This proposed method was successfully applied to commercial injection samples and emulsion cosmetics. The mechanism of CL reaction was also studied.

Fluorescence enhancement effect of morin-nucleic acid-L-cysteine-capped nano-ZnS system and the determination of nucleic acid.

It is found that L-cysteine-capped nano-ZnS can further enhance the fluorescence intensity of the morin-nucleic acid system. Under optimum conditions, the enhanced intensity of fluorescence is proportional to the concentration of nucleic acid in the range of 7.0 x 10(-8)-1.0 x 10(-5) g mL(-1) for fish sperm DNA (fsDNA) and 9.0 x 10(-8)-5.0 x 10(-6) g mL(-1) for yeast RNA (yRNA). The corresponding detection limits (S/N = 3) are 2.0 x 10(-8) g mL(-1) and 4.0 x 10(-8) g mL(-1), respectively. The interaction mechanisms of morin-nucleic acid-L-cysteine-capped nano-ZnS system are studied by multiple techniques. It is considered that there exists synergistic effects of groove binding and electrostatic interaction between morin, L-cysteine-capped nano-ZnS and nucleic acid, and the complex of morin-L-cysteine-capped nano-ZnS-nucleic acid is formed.

Scopoletine as fluorescence probe for determination of protein.

Scopoletine (SLT), 7-hydroxy-6-methoxylcoumarin, is known to possess biological activities such as abirritating and anti-tumor, it can quench intrinsic fluorescence of bovine serum albumin (BSA) and the fluorescence intensity of itself is enhanced. So, SLT is used as fluorescence probe for quantitative determination of protein. The experiments indicate that under optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of proteins in a wide range, and their detection limits (S/N=3) are 1.4 x 10(-8)g mL(-1) for BSA and 1.1 x 10(-8)g mL(-1) for HSA, respectively. Samples were satisfactorily determined. The interaction mechanism is also discussed.

Flow injection-chemiluminescence determination of phenol using potassium permanganate and formaldehyde system.

It is found that phenol can react with potassium permanganate in the acidic medium and produce chemiluminescence, which is greatly enhanced by formaldehyde. The optimum conditions for this chemiluminescent reaction are in detail studied using a flow injection system. The experiments indicate that under optimum conditions, the chemiluminescence intensity is linearly related to the concentration of phenol in the range 5.0x10(-9) to 1.0x10(-6)gmL-1 with a detection limit (3sigma) of 3x10(-9)gmL-1. The relative standard deviation is 1.2% for 4.0x10(-7)gmL-1 phenol solution in 11 repeated measurements. This method has the advantages of simple operation, fast response and high sensitivity. The method is successfully applied to the determination of phenol in the waste water.

Improvement of the acridine orange-protein-surfactant system for protein estimation based on aromatic ring stacking effect of sodium dodecyl benzene sulphonate.

The fluorescence of acridine orange (AO) is greatly quenched by the anionic surfactant sodium dodecyl benzene sulphonate (SDBS), but when protein is added into the AO-SDBS system, the fluorescence intensity of the latter is enhanced again. Based on this, a new fluorimetric method of determination of protein was developed. Under optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of protein, such as bovine serum albumin (BSA), human serum albumin (HSA) and egg albumin (EA), over a wide range with detection limits at the 10(-9) g/mL level. This method has been satisfactorily used for the determination of protein in samples. We compared results using 280 nm and 490 nm excitation wavelengths and the mechanism of the assay.

Fluorescence enhancement of the protein-curcumin-sodium dodecyl benzene sulfonate system and protein determination.

Protein can greatly enhance the fluorescence of curcumin (CU) in the presence of sodium dodecyl benzene sulfonate (SDBS). Experiments indicate that under the optimum conditions, the enhanced intensity of fluorescence is proportional to the concentration of proteins in the range of 0.0050-20.0 microg mL(-1) for bovine serum albumin (BSA), 0.080-20.0 microg mL(-1) for human serum albumin (HSA), and 0.040-28.0 microg mL(-1) for egg albumin (EA). Their detection limits (S/N = 3) are 1.4 ng mL(-1), 20 ng mL(-1), and 16 ng mL(-1), respectively. The method has been satisfactorily used for the determination of proteins in actual samples. In comparison with most of fluorimetric methods, this method is quick and simple, has high sensitivity and good stability. The interaction mechanism is also studied.

Study on the formation and depolymerization of acridine orange dimer in acridine orange-sodium dodecyl benzene sulfonate-protein system.

Experiment indicates that the fluorescence of acridine orange (AO) can be greatly quenched by anionic surfactant sodium dodecyl benzene sulfonate (SDBS), but when protein is added into the AO-SDBS system, the fluorescence intensity of the latter is enhanced. It is considered that SDBS can promote the formation of AO dimer, resulting in the quenching of the fluorescence of AO. When bovine serum albumin (BSA) is added into AO-SDBS system, BSA and SDBS can interact and form negative micelle-like cluster complex with "aromatic ring stacking," which destroys the formation conditions of AO dimer and makes some AO dimers turn into monomer, resulting in the fluorescence enhancement of AO-SDBS system. Whereas the positive AO and residual AO dimer are dissolved in the negative BSA-SDBS cluster through electrostatic and hydrophobic forces and form a large association. Here, the fluorescence enhancement of AO-SDBS is considered to originate from the hydrophobic microenvironment provided by BSA and SDBS, the depolymerization of AO dimer and intermolecular energy transfer between BSA and AO.

Fluorescence enhancement effect of the morin-Al3+ -sodium dodecyl benzene sulphonate-protein system and the determination of proteins.

The fluorescence intensity of the morin-Al(3+) complex was greatly enhanced by proteins in the presence of sodium dodecyl benzene sulphonate (SDBS). Based on this, a new fluorimetric method for the determination of protein was developed. Under optimum conditions, the enhanced intensity of fluorescence was in proportion to the concentration of proteins in the range 1.0 x 10(-8)-1.3 x 10(-5) g/mL for bovine serum albumin (BSA), 4.0 x 10(-8)-1.2 x 10(-5) g/mL for egg albumin (EA) and 5.0 x 10(-8)-1.2 x 10(-5) g/mL for human serum albumin (HSA). Their detection limits (S:N = 3) were 5.0 x 10(-9), 1.8 x 10(-8) and 1.6 x 10(-8) g/mL, respectively. The interaction mechanism was also studied.

A fluorimetric method for the determination of nucleic acids using Ce(IV) and sodium triphosphate.

A novel and stable fluorimetric method was established for the determination of nucleic acids. The proposed method is based on the reduction by nucleic acids of Ce(IV) to fluorescent Ce(III). The fluorescence intensity can be greatly increased by sodium triphosphate. The enhanced fluorescence intensity is proportional to the concentration of nucleic acids in the range 4.2 x 10(-8)-4.2 x 10(-6) g/mL for fish sperm DNA and 5.0 x 10(-8)-6.5 x 10(-6) g/mL for yeast RNA, and the detection limits (S/N = 3) are 13.5 ng/mL and 45 ng/mL, respectively. The reaction mechanism of the hydrolytic scission of nucleic acids by Ce(IV) is discussed.

Flow injection-chemiluminescence determination of amoxycillin using potassium permanganate and formaldehyde system.

It was found that amoxycillin can react with potassium permanganate in an acidic medium to produce chemiluminescence, which is greatly enhanced by formaldehyde. The optimum conditions for this chemiluminescent reaction were studied in detail using a flow-injection system. The experimental results indicate that, under optimum conditions, the chemiluminescence intensity is linearly related to the concentration of amoxycillin in the range 5.48 x 10(-8)-2.74 x 10(-6) mol/L, with a detection limit (3sigma) of 4.1 x 10(-8) mol/L. The relative standard deviation was 1.0% at 1.1 x 10(-6) mol/L amoxycillin (n = 11 measurements). This method has the advantages of high sensitivity, fast response and ease of operation. The method was successfully applied to the determination of amoxycillin in raw medicines and capsules.

The fluorescence enhancement effect of Tb-Gd-adenosine triphosphate-phen system and its analytical application.

It is found that the fluorescence of Tb-adenosine triphosphate (ATP)-phenanthroline (phen) system can be enhanced by Gd(3+). The fluorescence enhancement of the Tb-Gd-ATP-phen system is considered to originate from intramolecular and intermolecular energy transfers, and the energy-insulating sheath effect of Gd-ATP-phen complex. In addition, a new energy transfer pathway in Tb-ATP-phen system is proposed. As a mediator, phen can transfer the energy absorbed by ATP to Tb(3+) through the stacking action between aromatic ring of phen and purine ring of ATP. The proposed method has been used to determine trace amount of ATP. The detection limit is 5.4 x 10(-9)mol/l, which is about 40 times lower than that of the Tb-ATP-phen system. The proposed method is one of the most sensitive fluoremetries of ATP.

Sensitive determination of carbohydrates by fluorimetric method with Ce(IV) and sodium triphosphate.

A new simple and sensitive fluorimetric method for the determination of carbohydrates is described. The method is based on the reaction between carbohydrates and Ce(IV) in the presence of sulfuric acid. All the reductive carbohydrates can be detected indirectly by the fluorescence of Ce(III) produced. The addition of sodium triphate enhances the sensitivity of the method by more than 10-folds. Under optimum conditions, an excellent linear relationship was obtained between the fluorescence intensity and the concentration of carbohydrates. The limits of detection lie in the range of 9.3 x 10(-10) - 1.3 x 10(-9) mol/L. As compared to the normal fluorimetric method, the proposed method is faster and more sensitive.

Study on the fluorescent enhancement effect in terbium-gadolinium-protein-sodium dodecyl benzene sulfonate system and its application on sensitive detection of protein at nanogram level.

The co-luminescence effect in a terbium-gadolinium-protein-sodium dodecyl benzene sulfonate (SDBS) system is reported here. Based on it, the sensitive quantitative analysis of protein at nanogram levels is established. The co-luminescence mechanism is studied using fluorescence, resonance light scattering (RLS), absorption spectroscopy and NMR measurement. It is considered that protein could be unfolded by SDBS, then a efficacious intramolecular fluorescent energy transfer occurs from unfolded protein to rare earth ions through SDBS acting as a "transfer bridge" to enhance the emission fluorescence of Tb3+ in this ternary complex of Tb-SDBS-BSA, where energy transfer from protein to SDBS by aromatic ring stacking is the most important step. Cooperating with the intramolecular energy transfer above is the intermolecular energy transfer between the simultaneous existing complexes of both Tb3+ and Gd3+. The fluorescence quantum yield is increased by an energy-insulating sheath, which is considered to be another reason for the resulting enhancement of the fluorescence. Förster theory is used to calculate the distribution of enhancing factors and has led to a greater understanding of the mechanisms of energy transfer.

Analysis of tryptophan at nmoll(-1) level based on the fluorescence enhancement of terbium-gadolinium-tryptophan-sodium dodecyl benzene sulfonate system.

It is found that Tb(3+) can react with tryptophan (Trp) and sodium dodecyl benzene sulfonate (SDBS), and emits the intrinsic fluoresence of Tb(3+). The fluorescence intensity can be enhanced by La(3+), Gd(3+), Lu(3+), Sc(3+) and Y(3+), among which Gd(3+) has the greatest enhancement. This is a new co-luminescence system. The studies indicate that in the Tb-Gd-Trp-SDBS system, there is both Tb-Trp-SDBS and Gd-Trp-SDBS complexes, and they aggregate together and form a large congeries. The fluorescence enhancement of the Tb-Gd-Trp-SDBS system is considered to originate from intramolecular and intermolecular energy transfers, and the energy-insulating sheath effect of Gd-Trp-SDBS complex. Under the optimum conditions, the enhanced intensity of fluorescence is in proportion to the concentration of Trp in the range from 4x10(-8) to 4x10(-5)moll(-1). The detection limit is 10(-9)moll(-1). The proposed method is one of the most sensitive fluoremetries of Trp.

Resonance light-scattering method for the determination of BSA and HSA with sodium dodecyl benzene sulfonate or sodium lauryl sulfate.

A new resonance light-scattering (RLS) assay of proteins such as bovine serum albumin (BSA) and human serum albumin (HSA) is presented. In the medium of phosphoric acid (pH=2.6), the weak RLS of sodium dodecyl benzene sulfonate (SDBS) or sodium lauryl sulfate (SLS) can be greatly enhanced by proteins, owing to interaction between the protein and the anionic surfactant and formation of an associate. The RLS intensity of the SDBS-protein system is stronger than that of the SLS-protein system under same experimental conditions. It is considered that the synergistic resonance caused by the absorption of both protein and SDBS could produce strong RLS, while absorption of protein only in the SLS system could cause relatively weak RLS. The enhanced intensity of RLS is proportional to the concentration of the protein. If SDBS is used as the probe the linear range is 7.5 x 10(-9)-1.5 x 10(-5) g mL(-1) for BSA and 1.0 x 10(-8)-1.0 x 10(-5) g mL(-1) for HSA. The detection limits are 1.8 and 2.8 ng mL(-1), respectively. When SLS is used as the probe the linear range is 2.0 x 10(-8)-1.0 x 10(-5) g mL(-1) and 2.5 x 10(-8)-1.0 x 10(-5) g mL(-1) for BSA and HSA, respectively, and the detection limits are 12.8 and 21.6 ng mL(-1), respectively. The biological mimics samples are synthetic concoctions of BSA and HSA with some interferents. In these samples, the concentration of interferents is higher than the concentration normally existing in organisms. The samples were determined satisfactorily.