Coupling capillary electrophoresis with mass spectrometry for the analysis of oxidized phospholipids in human high-density lipoproteins.

The oxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine (ox-PAPC) products in human high-density lipoproteins (HDLs) were investigated by low-flow capillary electrophoresis-mass spectrometry (low-flow CE-MS). To accelerate the optimization, native PAPC (n-PAPC) standard was first analyzed by a commercial CE instrument with a photodiode array detector. The optimal separation buffer contained 60% (v/v) acetonitrile, 40% (v/v) methanol, 20 mM ammonium acetate, 0.5% (v/v) formic acid, and 0.1% (v/v) water. The selected separation voltage and capillary temperature were 20 kV and 23°C. The optimal CE separation buffer was then used for the low-flow CE-MS analysis. The selected MS conditions contained heated capillary temperature (250°C), capillary voltage (10 V), and injection time (1 s). No sheath gas was used for MS. The linear range for n-PAPC was 2.5-100.0 µg/mL. The coefficient of determination (R2 ) was 0.9918. The concentration limit of detection was 1.52 µg/mL, and the concentration limit of quantitation was 4.60 µg/mL. The optimal low-flow CE-MS method showed good repeatability and sensitivity. The ox-PAPC products in human HDLs were determined based on the in vitro ox-PAPC products of n-PAPC standard. Twenty-one ox-PAPC products have been analyzed in human HDLs. Uremic patients showed significantly higher levels of 15 ox-PAPC products than healthy subjects.

Determination of oxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine products in human very low-density lipoproteins by nonaqueous low-flow capillary electrophoresis-mass spectrometry.

A simple and fast low-flow capillary electrophoresis-mass spectrometry (low-flow CE-MS) method has been developed to analyze oxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine (ox-PAPC) products in human very low-density lipoproteins (VLDLs). Native PAPC standard was analyzed to optimize the low-flow CE-MS method. The optimal CE conditions included separation buffer (60% (v/v) acetonitrile, 40% (v/v) methanol, 0.1% (v/v) water, 0.5% (v/v) formic acid, 20 mM ammonium acetate), sheath liquid (60% (v/v) acetonitrile, 40% (v/v) methanol, 0.1% (v/v) water, 20 mM ammonium acetate), separation voltage (20 kV), separation capillary internal diameter (i.d.) (75 µm), separation capillary temperature (23˚C) and sample injection time (6 s). The selected MS conditions included heated capillary temperature (250°C), capillary voltage (10 V), and injection time (1 s). Sheath gas was not used in this study. The total ion chromatograms (TICs), extracted ion chromatograms (EICs) and MS spectra of native PAPC standard and its in vitro oxidation products showed good repeatability and sensitivity. To determine the ox-PAPC products in human VLDLs, the EICs and MS spectra of VLDLs were compared with the in vitro oxidation products of native PAPC standard. For native PAPC standard, the measured linear range was 2.5 - 100.0 µg/mL, and the coefficients of determination (R2) was 0.9994. The concentration limit of detection (LOD) was 0.44 µg/mL, and the concentration limit of quantitation (LOQ) was 1.34 µg/mL. A total of 21 ox-PAPC products were analyzed for the VLDLs of healthy and uremic subjects. The levels of 7 short-chain and 5 long-chain ox-PAPC products on uremic VLDLs were significantly higher than healthy VLDLs. This simple low-flow CE-MS method might be a good alternative for LC-MS for the analysis of ox-PAPC products. Furthermore, it might also help scientists to expedite the search for uremic biomarkers.

Electrochemical ammonia synthesis from nitrite assisted by in situ generated hydrogen atoms on a nickel phosphide catalyst.

Investigating green and effective means for ammonia synthesis is an important but challenging task. Electrochemical ammonia synthesis (EAS) from an indirect route (N2 → NOx → NH3) provides a feasible alternative strategy. The key step in this route is the reduction of NOx to NH3 instead of N2, which requires the investigation of efficient catalysts with high selectivity of NH3. Herein, we initially demonstrate a highly efficient electrochemical reduction of NO2- to NH3 with nickel phosphide (Ni2P) as the catalyst. The system exhibits low onset potential (0.2 V vs. RHE) and high faradaic efficiency (>90%) for EAS. Experimental results and theoretical calculations reveal that the in situ generated hydrogen atoms on the surface of Ni2P greatly promote the reduction of NO2- to NH3.

Visible light driven photo-reduction of Cu2+ to Cu2O to Cu in water for photocatalytic hydrogen production.

Metal nanoparticles are synthesized via various methods and have found many applications in areas such as sensing, electronics and catalysis. Light induced formation of noble metal nanoparticles, especially platinum, in solution or loaded on semiconductor surfaces, is an established practice in photocatalysis. Nevertheless, preparation of catalytically-active non-precious metal nanoparticles via photo-reduction still have room to be further explored. Here, we report a visible light driven system that can coordinate photo-reduction of CuSO4 to selectively prepare Cu2O or Cu nanoparticles, while at the same time, mediating efficient hydrogen production with in situ generating Cu catalyst without further need to add any components. The Cu2O and Cu nanoparticles in situ generated are crystalline in nature and can perform as pre-catalyst (Cu2O) or catalyst (Cu) to catalyze hydrogen production when reincorporated into the same photo-reduction system with organic photosensitizers. Our work offers an exploratory pathway to prepare target metal nanoparticles while provides some insight into harnessing solar energy for multi-functional purposes.

Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

Cu(OH)2 supported on Fe(OH)3 as a synergistic and highly efficient system for the dehydrogenation of ammonia-borane.

Herein, we first describe the physical mixture of Cu(OH)2/Fe(OH)3 as a composite catalyst precursor for the dehydrogenation of ammonia borane (AB) in methanol. During the initial period of catalytic reaction, Cu nanoparticles were formed in-situ. The catalytic activity of Cu nanoparticles can be significantly enhanced with the assistance of Fe species and OH-. A maximum turnover frequency (TOF) of 50.3 molH2 moltotal metal-1 min-1 (135.6 molH2 molCu-1 min-1) was achieved at ambient temperature, which is superior to those of previously reported Fe or Cu based systems.

Metal Phosphides as Co-Catalysts for Photocatalytic and Photoelectrocatalytic Water Splitting.

Solar-to-hydrogen conversion based on photocatalytic and photoelectrocatalytic water splitting is considered as a promising technology for sustainable hydrogen production. Developing earth-abundant H2 -production materials with robust activity and stability has become the mainstream in this field. Due to the unique properties and characteristics, transition metal phosphides (TMPs) have been proven to be high performance co-catalysts to replace some of the classic precious metal materials in photocatalytic water splitting. In this Minireview, we summarize the recent significant progress of TMPs as cocatalysts for water splitting reaction with high activity and stability. Firstly, the characteristic of TMPs is briefly introduced. Then, we mainly discuss the recent research efforts toward their application as photocatalytic co-catalysts in photocatalytic H2 -production, O2 -evolution and photoelectrochemical water splitting. Finally, the catalytic mechanism, current existing challenges and future working directions for improving the performance of TMPs are proposed.

Rapid synthesis of ultralong Fe(OH)3:Cu(OH)2 core-shell nanowires self-supported on copper foam as a highly efficient 3D electrode for water oxidation.

One-dimensional core-shell nanowire materials have recently received great attention as durable catalysts for water splitting. Herein we report the facile and rapid synthesis of ultralong Fe(OH)3:Cu(OH)2 core-shell nanowires grown in situ on an open 3D electrode to function as a highly efficient electrocatalyst for water oxidation. It only requires an overpotential of ∼365 mV to reach a 10 mA cm-2 current density in 1.0 M KOH. As far as we know, this shows the best result amongst Cu-based heterogeneous OER systems reported to date.

Self-Supported Cedarlike Semimetallic Cu3P Nanoarrays as a 3D High-Performance Janus Electrode for Both Oxygen and Hydrogen Evolution under Basic Conditions.

There has been strong and growing interest in the development of cost-effective and highly active oxygen evolution reaction (OER) electrocatalysts for alternative fuels utilization and conversion devices. We report herein that semimetallic Cu3P nanoarrays directly grown on 3D copper foam (CF) substrate can function as effective electrocatalysts for water oxidation. Specifically, the surface oxidation-activated Cu3P only required a relatively low overpotential of 412 mV to achieve a current density of 50 mA cm(-2) and displayed a small Tafel slope of 63 mV dec(-1) in 0.1 M KOH solution, on account of the collaborative effect of large roughness factor (RF) and semimetallic character. Following that, investigations into the mechanism revealed the formation of a unique active phase during the water oxidation process in which conductive Cu3P was the core covered with a thin copper oxide/hydroxide layer. Moreover, this Cu3P 3D electrode was also applied to the hydrogen evolution reaction (HER) and showed good catalytic performance and stability under the same basic conditions.

Spectacular photocatalytic hydrogen evolution using metal-phosphide/CdS hybrid catalysts under sunlight irradiation.

A highly efficient and robust heterogeneous photocatalytic hydrogen evolution system was established for the first time by using the CoP/CdS hybrid catalyst in water under solar irradiation. The H2-production rate can reach up to 254,000 µmol h(-1) g(-1) during 4.5 h of sunlight irradiation, which is one of the highest values ever reported on CdS photocatalytic systems in the literature.

Photochemical, electrochemical, and photoelectrochemical water oxidation catalyzed by water-soluble mononuclear ruthenium complexes.

Two mononuclear ruthenium complexes [Ru(H2tcbp)(isoq)2] (1) and [Ru(H2tcbp)(pic)2] (2) (H4tcbp=4,4',6,6'-tetracarboxy-2,2'-bipyridine, isoq=isoquinoline, pic=4-picoline) are synthesized and fully characterized. Two spare carboxyl groups on the 4,4'-positions are introduced to enhance the solubility of 1 and 2 in water and to simultaneously allow them to tether to the electrode surface by an ester linkage. The photochemical, electrochemical, and photoelectrochemical water oxidation performance of 1 in neutral aqueous solution is investigated. Under electrochemical conditions, water oxidation is conducted on the deposited indium-tin-oxide anode, and a turnover number higher than 15,000 per water oxidation catalyst (WOC) 1 is obtained during 10 h of electrolysis under 1.42 V vs. NHE, corresponding to a turnover frequency of 0.41 s(-1). The low overpotential (0.17 V) of electrochemical water oxidation for 1 in the homogeneous solution enables water oxidation under visible light by using [Ru(bpy)3](2+) (P1) (bpy=2,2'-bipyridine) or [Ru(bpy)2(4,4'-(COOEt)2-bpy)](2+) (P2) as a photosensitizer. In a three-component system containing 1 or 2 as a light-driven WOC, P1 or P2 as a photosensitizer, and Na2S2O8 or [CoCl(NH3)5]Cl2 as a sacrificial electron acceptor, a high turnover frequency of 0.81 s(-1) and a turnover number of up to 600 for 1 under different catalytic conditions are achieved. In a photoelectrochemical system, the WOC 1 and photosensitizer are immobilized together on the photoanode. The electrons efficiently transfer from the WOC to the photogenerated oxidizing photosensitizer, and a high photocurrent density of 85 µA cm(-2) is obtained by applying 0.3 V bias vs. NHE.

Highly efficient photocatalytic hydrogen evolution by nickel phosphide nanoparticles from aqueous solution.

Monodispersed nickel phosphide (Ni2P) nanoparticles were for the first time applied to photocatalytic hydrogen evolution from lactic acid aqueous solution under visible light LED irradiation using CdS nanorods as a photosensitizer. The system exhibited high photocatalytic hydrogen-generating activity and excellent stability in aqueous acidic media.

Photoreduction of iron(III) to iron(0) nanoparticles for simultaneous hydrogen evolution in aqueous solution.

Crystalline Fe nanoparticles were obtained with fluorescein (Fl) as the photosensitizer in triethylamine (TEA) or triethanolamine (TEOA) aqueous solution with FeCl3 as the Fe precursor under bright visible-light light-emitting diode (LED) irradiation. Photoinduced electron transfer from excited state Fl* and Fl(-) to Fe(3+) produced the Fe nanoparticles, which served as the active catalyst for in situ photocatalytic hydrogen production with Fl and TEA or TEOA as the photosensitizer and electron donors, respectively, in the same system. Robust hydrogen production activities were observed under the Fe nanoparticle photoreduction conditions in basic solution, and tens of milliliters of hydrogen were obtained over prolonged LED irradiation. If inorganic support materials such as NH2 -MCM-41 or reduced graphene oxide were introduced, dispersed nanoparticles with different sizes and shapes were deposited on the supports, which led to variously enhanced hydrogen production activities. The relationships between the morphologies of the Fe/H2 N-MCM-41 or Fe/graphene composites generated in situ and the hydrogen production activities were investigated systematically.

Efficient water oxidation catalyzed by mononuclear ruthenium(II) complexes incorporating Schiff base ligands.

Four new charge-neutral ruthenium(II) complexes containing dianionic Schiff base and isoquinoline or 4-picoline ligands were synthesized and characterized by NMR and ESI-MS spectroscopies, elemental analysis, and X-ray diffraction. The complexes exhibited excellent chemical water oxidation activity and high stability under acidic conditions (pH 1.0) using (NH4)2Ce(NO3)6 as a sacrificial electron acceptor. The high catalytic activities of these complexes for water oxidation were sustained for more than 10 h at low concentrations. High turnover numbers of up to 3200 were achieved. A water nucleophilic attack mechanism was proposed. A Ru(V)=O intermediate was detected during the catalytic cycle by high-resolution mass spectrometry.