Electronic Structure Regulation by Fe Doped Ni-Phosphides for Long-term Overall Water Splitting at Large Current Density.

Acquiring a highly efficient electrocatalyst capable of sustaining prolonged operation under high current density is of paramount importance for the process of electrocatalytic water splitting. Herein, Fe-doped phosphide (Fe-Ni5P4) derived from the NiFc metal-organic framework (NiFc-MOF) (Fc: 1,1'-ferrocene dicarboxylate) shows high catalytic activity for overall water splitting (OWS). Fe-Ni5P4||Fe-Ni5P4 exhibits a low voltage of 1.72 V for OWS at 0.5 A cm-2 and permits stable operation for 2700 h in 1.0 m KOH. Remarkably, Fe-Ni5P4||Fe-Ni5P4 can sustain robust water splitting at an extra-large current density of 1 A cm-2 for 1170 h even in alkaline seawater. Theoretical calculations confirm that Fe doping simultaneously reduces the reaction barriers of coupling and desorption (O*→OOH*, OOH*→O2 *) in the oxygen evolution reaction (OER) and regulates the adsorption strength of the intermediates (H2O*, H*) in the hydrogen evolution reaction (HER), enabling Fe-Ni5P4 to possess excellent dual functional activity. This study offers a valuable reference for the advancement of highly durable electrocatalysts through the regulation derived from coordination frameworks, with significant implications for industrial applications and energy conversion technologies.

Association between Blood Urea Nitrogen Level and In-Hospital Mortality in Patients with Acute Myocardial Infarction and Subsequent Gastrointestinal Bleeding.

Background: Limited studies have explored the association between blood urea nitrogen (BUN) levels and in-hospital mortality in patients with acute myocardial infarction (AMI) and subsequent gastrointestinal bleeding (GIB). Our objective was to explore this correlation. Methods: 276 individuals with AMI and subsequent GIB were retrospectively included between January 2012 and April 2023. The predictive value of BUN for in-hospital mortality was assessed through receiver operating characteristic (ROC) curve. Logistic regression models were constructed to assess the relationship between BUN and in-hospital mortality. Propensity score weighting (PSW), sensitivity and subgroup analyses were used to further explore the association. Results: Fifty-three (19.2%) patients died in the hospital. BUN levels were higher in non-survivors compared with the survivors [(11.17 ± 6.17) vs (8.09 ± 4.24), p = 0.001]. The ROC curve suggested that the optimal cut-off for BUN levels to predict in-hospital mortality was 8.45 mmol/L (AUC [area under the ROC curve] 0.678, 95% confidence interval [CI] 0.595-0.761, p < 0.001). Multivariable logistic regression showed that elevated BUN levels ( ≥ 8.45 mmol/L) were positively association with in-hospital mortality (odds ratio [OR] 4.01, 95% CI 1.55-10.42, p = 0.004). After PSW, sensitivity and subgroup analyses, the association remained significant. Conclusions: Elevated BUN levels were associated with in-hospital mortality in patients with AMI and subsequent GIB.

Ultrafine Ru nanoparticles stabilized by V8C7/C for enhanced hydrogen evolution reaction at all pH.

The development of cost-effective electrocatalysts with high efficiency and long durability for hydrogen evolution reaction (HER) remains a great challenge in the field of water splitting. Herein, we design an ultrafine and highly dispersed Ru nanoparticles stabilized on porous V8C7/C matrix via pyrolysis of the metal-organic frameworks V-BDC (BDC: 1,4-benzenedicarboxylate). The obtained Ru-V8C7/C composite exhibits excellent HER performance in all pH ranges. At the overpotential of 40 mV, its mass activity is about 1.9, 4.1 and 9.4 times higher than that of commercial Pt/C in acidic, neutral and alkaline media, respectively. Meanwhile, Ru-V8C7/C shows the remarkably high stability in all pH ranges which, in particular, can maintain the current density of 10 mA cm-2 for over 150 h in 1.0 mol L-1 phosphate buffer saline (PBS). This outstanding HER performance can be attributed to the high intrinsic activity of Ru species and their strong interface interactions to the V8C7/C substrate. The synergistic effect of abundant active sites on the surface and the formed Ru-C-V units at the interface promotes the adsorption of reaction intermediates and the release of active sites, contributing the fast HER kinetics. This work provides a reference for developing versatile and robust HER catalysts by surface and interface regulation for pH tolerance.

Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N-doped Carbon.

How to transfer industrial exhaust gases of nitrogen oxides into high-values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis of essential α-amino acids from nitric oxide (NO) by reacting with α-keto acids through electrocatalytic process with atomically dispersed Fe supported on N-doped carbon matrix (AD-Fe/NC) as the catalyst. A yield of valine with 32.1 µmol mgcat -1 is delivered at -0.6 V vs. reversible hydrogen electrode, corresponding a selectivity of 11.3 %. In situ X-ray absorption fine structure and synchrotron radiation infrared spectroscopy analyses show that NO as nitrogen source converted to hydroxylamine that promptly nucleophilic attacked on the electrophilic carbon center of α-keto acid to form oxime and subsequent reductive hydrogenation occurred on the way to amino acid. Over 6 kinds of α-amino acids have been successfully synthesized and gaseous nitrogen source can be also replaced by liquid nitrogen source (NO3 - ). Our findings not only provide a creative method for converting nitrogen oxides into high-valued products, which is of epoch-making significance towards artificial synthesis of amino acids, but also benefit in deploying near-zero-emission technologies for global environmental and economic development.

Ir Nanoparticles Anchored on Metal-Organic Frameworks for Efficient Overall Water Splitting under pH-Universal Conditions.

The construction of high-activity and low-cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst by anchoring well-dispersed Ir nanoparticles on nickel metal-organic framework (MOF) Ni-NDC (NDC: 2,6-naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between Ir and MOF through interfacial Ni-O-Ir bonds, the synthesized Ir@Ni-NDC showed exceptional electrocatalytic performance for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting in a wide pH range, superior to commercial benchmarks and most reported electrocatalysts. Theoretical calculations revealed that the charge redistribution of Ni-O-Ir bridge induced the optimization of H2 O, OH* and H* adsorption, thus leading to the accelerated electrochemical kinetics for HER and OER. This work provides a new clue to exploit bifunctional electrocatalysts for pH-universal overall water splitting.

Redox-Active Mixed-Linker Metal-Organic Frameworks with Switchable Semiconductive Characteristics for Tailorable Chemiresistive Sensing.

Metal-organic frameworks (MOFs), with diverse metal nodes and designable organic linkers, offer unique opportunities for the rational engineering of semiconducting properties. In this work, we report a mixed-linker conductive MOF system with both tetrathiafulvalene and Ni-bis(dithiolene) moieties, which allows the fine-tuning of electronic structures and semiconductive characteristics. By continuously increasing the molar ratio between tetrathiafulvalene and Ni-bis(dithiolene), the switching of the semiconducting behaviors from n-type to p-type was observed along with an increase in electrical conductivity by 3 orders of magnitude (from 2.88×10-7  S m-1 to 9.26×10-5  S m-1 ). Furthermore, mixed-linker MOFs were applied for the chemiresistive detection of volatile organic compounds (VOCs), where the sensing performance was modulated by the corresponding linker ratios, showing synergistic and nonlinear modulation effects.

Critical role of hydrogen sorption kinetics in electrocatalytic CO2 reduction revealed by on-chip in situ transport investigations.

Precise understanding of interfacial metal-hydrogen interactions, especially under in operando conditions, is crucial to advancing the application of metal catalysts in clean energy technologies. To this end, while Pd-based catalysts are widely utilized for electrochemical hydrogen production and hydrogenation, the interaction of Pd with hydrogen during active electrochemical processes is complex, distinct from most other metals, and yet to be clarified. In this report, the hydrogen surface adsorption and sub-surface absorption (phase transition) features of Pd and its alloy nanocatalysts are identified and quantified under operando electrocatalytic conditions via on-chip electrical transport measurements, and the competitive relationship between electrochemical carbon dioxide reduction (CO2RR) and hydrogen sorption kinetics is investigated. Systematic dynamic and steady-state evaluations reveal the key impacts of local electrolyte environment (such as proton donors with different pKa) on the hydrogen sorption kinetics during CO2RR, which offer additional insights into the electrochemical interfaces and optimization of the catalytic systems.

On-Chip Investigation of Electrocatalytic Oxygen Reduction Reaction of 2D Materials.

The on-chip electrocatalytic microdevice (OCEM) is an emerging platform specialized in the electrochemical investigation of single-entity nanomaterials, which is ideal for probing the intrinsic catalytic properties, optimizing performance, and exploring exotic mechanisms. However, the current catalytic applications of OCEMs are almost exclusively in electrocatalytic hydrogen/oxygen evolution reactions with minimized influence from the mass transfer. Here, an OCEM platform specially tailored to investigate the electrocatalytic oxygen reduction reaction (ORR) at a microscopic level by introducing electrolyte convection through a microfluidic flow cell is reported. The setup is established on gold microelectrodes and later successfully applied to investigate how Ar-plasma treatment affects the ORR activities of 2H MoS2 . This study finds that Ar-plasma treatment significantly enhances the ORR performance of MoS2 nanosheets owing to the introduction of surface defects. This study paves the way for highly efficient microscopic investigation of diffusion-controlled electrocatalytic reactions.

The Critical Role of Initial/Operando Oxygen Loading in General Bismuth-Based Catalysts for Electroreduction of Carbon Dioxide.

Operando reconstruction of solid catalyst into a distinct active state frequently occurs during electrocatalytic processes. The correlation between initial and operando states, if ever existing, is critical for the understanding and precise design of a catalytic system. Inspired by recently established intermediate metallic state of Bi-based catalysts during electrocatalytic carbon dioxide reduction (CO2RR), here we investigate a series of Bi oxide catalysts (Bi, Bi2O3, BiO2) and demonstrate that the operando surface/subsurface oxygen loading, positively correlated to the initial oxygen content, plays a critical role in determining Bi-based CO2RR performance. Higher initial oxygen loading indicates a better electrocatalytic efficiency. Further analysis shows that this conclusion generally applies to all Bi-based electrocatalysts reported up to date. Following this principle, cost-effective BiO2 nanocrystals demonstrated the highest formate Faradaic efficiency (FE) and current density compared to Bi/Bi2O3, further allowing a pair-electrolysis system with 800 mA/cm2 current density and an overall 175% FE for formate production.

Boosting the performance of single-atom catalysts via external electric field polarization.

Single-atom catalysts represent a unique catalytic system with high atomic utilization and tunable reaction pathway. Despite current successes in their optimization and tailoring through structural and synthetic innovations, there is a lack of dynamic modulation approach for the single-atom catalysis. Inspired by the electrostatic interaction within specific natural enzymes, here we show the performance of model single-atom catalysts anchored on two-dimensional atomic crystals can be systematically and efficiently tuned by oriented external electric fields. Superior electrocatalytic performance have been achieved in single-atom catalysts under electrostatic modulations. Theoretical investigations suggest a universal "onsite electrostatic polarization" mechanism, in which electrostatic fields significantly polarize charge distributions at the single-atom sites and alter the kinetics of the rate determining steps, leading to boosted reaction performances. Such field-induced on-site polarization offers a unique strategy for simulating the catalytic processes in natural enzyme systems with quantitative, precise and dynamic external electric fields.