Precious-Metal-Free Mo-MXene Catalyst Enabling Facile Ammonia Synthesis Via Dual Sites Bridged by H-Spillover.

To date, NH3 synthesis under mild conditions is largely confined to precious Ru catalysts, while nonprecious metal (NPM) catalysts are confronted with the challenge of low catalytic activity due to the inverse relationship between the N2 dissociation barrier and NHx (x = 1-3) desorption energy. Herein, we demonstrate NPM (Co, Ni, and Re)-mediated Mo2CTx MXene (where Tx denotes the OH group) to achieve efficient NH3 synthesis under mild conditions. In particular, the NH3 synthesis rate over Re/Mo2CTx and Ni/Mo2CTx can reach 22.4 and 21.5 mmol g-1 h-1 at 400 °C and 1 MPa, respectively, higher than that of NPM-based catalysts and Cs-Ru/MgO ever reported. Experimental and theoretical studies reveal that Mo4+ over Mo2CTx has a strong ability for N2 activation; thus, the rate-determining step is shifted from conventional N2 dissociation to NH2* formation. NPM is mainly responsible for H2 activation, and the high reactivity of spillover hydrogen and electron transfer from NPM to the N-rich Mo2CTx surface can efficiently facilitate nitrogen hydrogenation and the subsequent desorption of NH3. With the synergistic effect of the dual active sites bridged by H-spillover, the NPM-mediated Mo2CTx catalysts circumvent the major obstacle, making NH3 synthesis under mild conditions efficient.

High quantum efficiency of hydrogen production from methanol aqueous solution with PtCu-TiO2 photocatalysts.

Methanol with 12.5 wt% H2 content is widely considered a liquid hydrogen medium. Taking into account water with 11.1 wt% H2 content, H2 synthesis from the mixture of water and methanol is a promising method for on-demand hydrogen production. We demonstrate an atomic-level catalyst design strategy using the synergy between single atoms and nanodots for H2 production. The PtCu-TiO2 sandwich photocatalyst achieves a remarkable H2 formation rate (2,383.9 µmol h-1) with a high apparent quantum efficiency (99.2%). Furthermore, the oxidation product is a high-value chemical formaldehyde with 98.6% selectivity instead of CO2, leading to a nearly zero-carbon-emission process. Detailed investigations indicate a dual role of the copper atoms: an electron acceptor to facilitate photoelectron transfer to Pt, and a hole acceptor for the selective oxidation of methanol to formaldehyde, thus avoiding over-oxidation to CO2. The synergy between Pt nanodots and Cu single atoms together reduces the activation energy of this process to 13.2 kJ mol-1.

Water-Promoted Carbon-Carbon Bond Cleavage Employing a Reusable Fe Single-Atom Catalyst.

The development of methods for selective cleavage reactions of thermodynamically stable C-C/C=C bonds in a green manner is a challenging research field which is largely unexplored. Herein, we present a heterogeneous Fe-N-C catalyst with highly dispersed iron centers that allows for the oxidative C-C/C=C bond cleavage of amines, secondary alcohols, ketones, and olefins in the presence of air (O2 ) and water (H2 O). Mechanistic studies reveal the presence of water to be essential for the performance of the Fe-N-C system, boosting the product yield from <1 % to >90 %. Combined spectroscopic characterizations and control experiments suggest the singlet 1 O2 and hydroxide species generated from O2 and H2 O, respectively, take selectively part in the C-C bond cleavage. The broad applicability (>40 examples) even for complex drugs as well as high activity, selectivity, and durability under comparably mild conditions highlight this unique catalytic system.

Atomic Insights into Synergistic Nitroarene Hydrogenation over Nanodiamond-Supported Pt1 -Fe1 Dual-Single-Atom Catalyst.

Fundamental understanding of the synergistic effect of bimetallic catalysts is of extreme significance in heterogeneous catalysis, but a great challenge lies in the precise construction of uniform dual-metal sites. Here, we develop a novel method for constructing Pt1 -Fe1 /ND dual-single-atom catalyst, by anchoring Pt single atoms on Fe1 -N4 sites decorating a nanodiamond (ND) surface. Using this catalyst, the synergy of nitroarenes selective hydrogenation is revealed. In detail, hydrogen is activated on the Pt1 -Fe1 dual site and the nitro group is strongly adsorbed on the Fe1 site via a vertical configuration for subsequent hydrogenation. Such synergistic effect decreases the activation energy and results in an unprecedented catalytic performance (3.1 s-1 turnover frequency, ca. 100 % selectivity, 24 types of substrates). Our findings advance the applications of dual-single-atom catalysts in selective hydrogenations and open up a new way to explore the nature of synergistic catalysis at the atomic level.

Exclusive Co-N4 Sites Confined in Two-dimensional Metal-Organic Layers Enabling Highly Selective CO2 Electroreduction at Industrial-Level Current.

Metal-organic framework catalysts bring new opportunities for CO2 electrocatalysis. Herein, we first conduct density-functional theory calculations and predict that Co-based porphyrin porous organic layers (Co-PPOLs) exhibit good activity for CO2 conversion because of the low *CO adsorption energy at Co-N4 sites, which facilitates *CO desorption and CO formation. Then, we prepare two-dimensional Co-PPOLs with exclusive Co-N4 sites through a facile surfactant-assisted bottom-up method. The ultrathin feature ensures the exposure of catalytic centers. Together with large specific area, high electrical conductivity and CO2 adsorption capability, Co-PPOLs achieve a peak faradaic efficiency for CO production (FECO =94.2 %) at a moderate potential in CO2 electroreduction, accompanied with good stability. Moreover, Co-PPOLs reach an industrial-level current above 200 mA in a membrane electrode assembly reactor, and maintain near-unity CO selectivity (FECO >90 %) over 20 h in CO2 electrolysis.

Potential-Driven Restructuring of Cu Single Atoms to Nanoparticles for Boosting the Electrochemical Reduction of Nitrate to Ammonia.

Restructuring is ubiquitous in thermocatalysis and of pivotal importance to identify the real active site, yet it is less explored in electrocatalysis. Herein, by using operando X-ray absorption spectroscopy in conjunction with advanced electron microscopy, we reveal the restructuring of the as-synthesized Cu-N4 single-atom site to the nanoparticles of ∼5 nm during the electrochemical reduction of nitrate to ammonia, a green ammonia production route upon combined with the plasma-assisted oxidation of nitrogen. The reduction of Cu2+ to Cu+ and Cu0 and the subsequent aggregation of Cu0 single atoms is found to occur concurrently with the enhancement of the NH3 production rate, both of them are driven by the applied potential switching from 0.00 to -1.00 V versus RHE. The maximum production rate of ammonia reaches 4.5 mg cm-2 h-1 (12.5 molNH3 gCu-1 h-1) with a Faradaic efficiency of 84.7% at -1.00 V versus RHE, outperforming most of the other Cu catalysts reported previously. After electrolysis, the aggregated Cu nanoparticles are reversibly disintegrated into single atoms and then restored to the Cu-N4 structure upon being exposed to an ambient atmosphere, which masks the potential-induced restructuring during the reaction. The synchronous changes of the Cu0 percentage and the ammonia Faradaic efficiency with the applied potential suggests that the Cu nanoparticles are the genuine active sites for nitrate reduction to ammonia, which is corroborated with both the post-deposited Cu NP catalyst and density functional theory calculations.

A risk score for early predicting bloodstream infections in febrile obstetric patients: a pilot study.

PURPOSE: Early prediction of bloodstream infections (BSI) among obstetric patients remains to be a challenge for clinicians. The objective of this study was to develop a risk score and assess its discriminative ability in febrile obstetric patients in a maternal intensive care unit (ICU). METHODS: Between May 2015 and August 2020, a total of 497 febrile obstetric patients were categorized into BSI group (n = 276) and Non-BSI group (n = 221) based on the result of blood cultures. White blood cell count, C-reactive protein (CRP), procalcitonin (PCT), time of interval from amniorrhea to fever (IFAF) and maximum body temperature (Tmax) were compared between the two groups. All patients were divided into training set (n = 298) and validation set (n = 199). The risk score was established using univariate and multivariate logistic regression from patients in the training set, and its discriminative ability was tested among patients in the validation set. RESULTS: The levels of neutrophil, CRP, PCT, IFAF and Tmax were significantly higher in BSI group than those in Non-BSI group. PROM, Tmax, neutrophil and CRP acted as independent predictive factors for BSI in the training set. The area under the receiver operating characteristic curve of risk score for early prediction of BSI in the training, validation set and the whole population was 0.829 (95% CI 0.783-0.876), 0.848 (95% CI 0.792-0.903) and 0.838 (95% CI 0.803-0.873), respectively. CONCLUSION: The risk score has a feasible discriminatory ability in early prediction of BSI in febrile obstetric patients.

Dynamic Behavior of Single-Atom Catalysts in Electrocatalysis: Identification of Cu-N3 as an Active Site for the Oxygen Reduction Reaction.

Atomically dispersed M-N-C (M refers to transition metals) materials represent the most promising catalyst alternatives to the precious metal Pt for the electrochemical reduction of oxygen (ORR), yet the genuine active sites in M-N-C remain elusive. Here, we develop a two-step approach to fabricate Cu-N-C single-atom catalysts with a uniform and well-defined Cu2+-N4 structure that exhibits comparable activity and superior durability in comparison to Pt/C. By combining operando X-ray absorption spectroscopy with theoretical calculations, we unambiguously identify the dynamic evolution of Cu-N4 to Cu-N3 and further to HO-Cu-N2 under ORR working conditions, which concurrently occurs with reduction of Cu2+ to Cu+ and is driven by the applied potential. The increase in the Cu+/Cu2+ ratio with the reduced potential indicates that the low-coordinated Cu+-N3 is the real active site, which is further supported by DFT calculations showing the lower free energy in each elemental step of the ORR on Cu+-N3 than on Cu2+-N4. These findings provide a new understanding of the dynamic electrochemistry on M-N-C catalysts and may guide the design of more efficient low-cost catalysts.

Fabrication of an Au25 -Cys-Mo Electrocatalyst for Efficient Nitrogen Reduction to Ammonia under Ambient Conditions.

Electrocatalysts for efficient production of ammonia from nitrogen reduction reaction (NRR) under ambient conditions are attracted growing interest in recent years, which demonstrate a great potential to replace the Haber-Bosch method which suffers the problems of the huge energy consumption and massive CO2 production. In this work, a novel electrocatalyst of Au25 -Cys-M is fabricated for NRR under ambient conditions, with transition metal ions (e.g., Mo6+ , Fe3+ , Co2+ , Ni2+ ) atomically decorated on Au25 nanoclusters via thiol bridging. The Au25 -Cys-Mo catalyst exhibits the highest Faradaic efficiency (26.5%) and NH3 yield (34.5 µg h-1  mgcat -1 ) in 0.1 m HCl solution. X-ray photoelectron spectroscopy analysis and high angle annular dark field image-scanning transmission electron microscopy characterization reveal that the electronic structure of Mo is optimized by forming the structure of Au-S-Mo and Mo acts as active sites for activating the nitrogen to promote the electrochemical production of ammonia. This work provides a new insight into the precise fabrication of efficient NRR electrocatalysts.

Cobalt Single Atoms on Tetrapyridomacrocyclic Support for Efficient Peroxymonosulfate Activation.

Transition-metal catalysts that can efficiently activate peroxide bonds have been extensively pursued for various applications including environmental remediation, chemical synthesis, and sensing. Here, we present pyridine-coordinated Co single atoms embedded in a polyaromatic macrostructure as a highly efficient peroxide-activation catalyst. The efficient catalytic production of reactive radicals through peroxymonosulfate activation was demonstrated by the rapid removal of model aqueous pollutants of environmental and public health concerns such as bisphenol A, without pH limitation and Co2+ leaching. The turnover frequency of the newly synthesized Co single-atom catalyst bound to tetrapyridomacrocyclic ligands was found to be 2 to 4 orders of magnitude greater than that of benchmark homogeneous (Co2+) and nanoparticulate (Co3O4) catalysts. Experimental results and density functional theory simulation suggest that the abundant π-conjugation in the polyaromatic support and strong metal-support electronic interaction allow the catalysts to effectively adsorb and activate the peroxide precursor. We further loaded the catalysts onto a widely used poly(vinylidene fluoride) microfiltration membrane and demonstrated that the model pollutants were oxidatively removed as they simply passed through the filter, suggesting the promise of utilizing this novel catalyst for realistic applications.

Highly efficient Co single-atom catalyst for epoxidation of plant oils.

Epoxidation of bio-derived plant oils is a sustainable route to manufacturing plasticizers, additives in lubricants, and other chemicals. The traditional synthetic approaches suffer from the employment of corrosive mineral acid or expensive peroxides (e.g., H2O2). In this work, we report the epoxidation of plant oils using O2 as the terminal oxidant catalyzed by Co-N-C/SiO2 single-atom catalyst. The single-atom dispersion of cobalt is confirmed by high-angle annular dark field-STEM and x-ray absorption fine structure techniques. In the epoxidation of methyl oleate under mild reaction conditions (35 °C, 0.1 MPa O2), 99% selectivity to the desired product is achieved at full conversion. Even for crude oils, Co-N-C/SiO2 is also effective and good yields of the corresponding epoxides are obtained. In addition, the catalyst is easily recovered and can be reused five times without obvious decay in catalytic activity/selectivity. A superoxide radical involved reaction mechanism is proposed on the basis of kinetic study and EPR experiment.

High-power and high-energy Nd:YAG-Nd:YVO4 hybrid gain Raman yellow laser.

We present a simple and reliable method to successfully reconcile the average output power and pulse energy of the solid-state Raman yellow lasers. By virtue of the hybrid laser gain of Nd:YAG and Nd:YVO4 in an intracavity frequency-doubled Raman, much higher pumping is allowed and nearly linear polarized fundamental and Stokes waves can be delivered for efficient non-critical phase matching. 7.6 W of yellow output at 588 nm is obtained under incident pump power of 42.0 W at the pulse repetition frequency (PRF) of 110 kHz and the pulse energy reaches 0.41 mJ under the same incident pump power at the PRF of 10 kHz.

Strong Metal-Support Interactions between Pt Single Atoms and TiO2.

Strong metal-support interaction (SMSI) has gained great attention in the field of heterogeneous catalysis. However, whether single-atom catalysts can exhibit SMSI remains unknown. Here, we demonstrate that SMSI can occur on TiO2 -supported Pt single atoms but at a much higher reduction temperature than that for Pt nanoparticles (NPs). Pt single atoms involved in SMSI are not covered by the TiO2 support nor do they sink into its subsurface. The suppression of CO adsorption on Pt single atoms stems from coordination saturation (18-electron rule) rather than the physical coverage of Pt atoms by the support. Based on the new finding it is revealed that single atoms are the true active sites in the hydrogenation of 3-nitrostyrene, while Pt NPs barely contribute to the activity since the NP sites are selectively encapsulated. The findings in this work provide a new approach to study the active sites by tuning SMSI.

A Hydrothermally Stable Irreducible Oxide-Modified Pd/MgAl2 O4 Catalyst for Methane Combustion.

Catalytic combustion is promising in removing trace amounts of CH4 to address serious environmental concerns. Supported Pd-based catalysts are most effective but often suffer from low stability in applications owing to the water-vapor-induced sintering. Herein, we develop a universal strategy to prepare irreducible-oxide-modified Pd/MgAl2 O4 catalysts which show high activity and excellent stability against both hydrothemal aging at elevated temperatures and deactivation in long-term reaction under wet conditions. The addition of irreducible oxides inhibited the deep oxidation of Pd in the oxygen-rich conditions, which preserved not only the epitaxial structure but also a suitable active phase of Pd-PdOx on MgAl2 O4 , thus promoting both activity and stability. This work provides new insights into the effect of metal-oxide interaction on CH4 combustion and offers an avenue to design hydrothermally stable and active combustion catalysts for industrial applications.

Observing the Viscous Relaxation Process of Silica Optical Fiber at ~1000 °C Using Regenerated Fiber Bragg Grating.

A regenerated fiber Bragg grating (RFBG) in silica fiber was used to observe the viscous relaxation process of the host silica fiber at high temperatures of around 1000 °C. Two factors, preannealing time and loaded tension, which affect viscous relaxation, were observed. When an RFBG is stretched after a longer preannealing, the measured viscosity of the optical fiber was observed to reach equilibrium faster, which means that preannealing accelerates viscous relaxation. A similar acceleration phenomenon was also observed when a larger load was applied to stretch the optical fiber, although the acceleration effect of loaded tension was not as strong as in the preannealing case. The results play an active role in establishing effective optical-fiber devices for application in high-temperature environments.

Temperature Self-Compensated Refractive Index Sensor Based on Fiber Bragg Grating and the Ellipsoid Structure.

In this paper, a temperature self-compensated refractive index sensor based on fiber Bragg grating (FBG) and the ellipsoid structure is demonstrated. The ellipsoid can excite the cladding modes and recouple them into the fiber core. Two well-defined wavelength bands are observed in the reflection spectrum of the proposed sensor, i.e., the Bragg resonant peak and the cladding resonant peaks. By measuring the wavelength shift of the cladding resonant peak, the surrounding refractive index (SRI) can be determined, and the wavelength shift of the Bragg resonant peak can be used as a reliable reference to self-compensate the temperature variation (temperature sensitivity of 10.76 pm/°C). When the SRI changes from 1.3352 to 1.3722, the cladding resonant peak redshifts linearly with an average sensitivity of 352.6 pm/RIU (refractive index unit). When the SRI changes from 1.3722 to 1.4426, an exponential redshift is observed with a maximum sensitivity of 4182.2 pm/RIU. Especially, the sensing performance is not very reliant on the distance between the FBG and the ellipsoid, greatly improving the ease of the fabrication.

Simultaneous Vector Bend and Temperature Sensing Based on a Polymer and Silica Optical Fibre Grating Pair.

The bending response of polymer optical fibre Bragg grating (POFBG) and silica optical fibre Bragg grating (SOFBG) mounted on a brass beam have been systematically studied and compared. The results indicate that POFBG has higher (almost twice as much) bend sensitivity than SOFBG. Based on the difference between the bend and temperature sensitivity of POFBG and SOFBG, a new method of measuring vector bend and temperature simultaneously was proposed by using a hybrid sensor head with series connection of one POFBG and one SOFBG with different Bragg wavelengths. It provides high sensitivity and resolution for sensing bend and temperature changes simultaneously and independently. The proposed sensor can find some applications in the fields where high sensitivity for both bend and temperature measurements are required.

Effect of retension sutures on abdominal pressure after abdominal surgery.

PURPOSE: To evaluate the effect of retention sutures on abdominal pressure and postoperative prognosis in abdominal surgery patients. METHODS: This prospective cohort study included patients who were admitted to Daping Hospital from May 15, 2014 to October 11, 2014. A total of 57 patients were enrolled, including 18 patients in the "U" type retention suture group, 17 patients in the intermittent retention suture group, and 22 patients in non-retention suture group. The demographic data, clinical data and risk factors for abdominal wound dehiscence were recorded. The bladder pressure (IVP) was monitored preoperatively, intraoperatively, and four days postoperatively. Additionally, the incidence of abdominal wound dehiscence and infection 14 days after the operation was recorded. RESULTS: During the operation, the IVP decreased and then increased; it was at its lowest 1 h after the start of the operation (5.3 mmHg ± 3.2 mmHg) and peaked after tension-reducing (8.8 mmHg ± 4.0 mmHg). The IVP values in the "U" type retention suture group and intermittent retention suture group were higher than in the non-retention suture group 4 days after operation (p < 0.005). The Visual Analogue Scale (VAS) pain scores were 3.9 ± 2.2, 3.8 ± 2.0, and 3.0 ± 1.0 in the retention suture group, intermittent retention suture group and non-retention suture group, respectively. The VAS pain scores in the "U" type tension-reducing group and intermittent tension-reducing group were higher than in the non-tension-reducing group (p < 0.005). CONCLUSION: Although retention sutures may reduce the incidence of postoperative wound dehiscence in abdominal surgery patients, they can increase the IVP and postoperative pain.

A Durable Nickel Single-Atom Catalyst for Hydrogenation Reactions and Cellulose Valorization under Harsh Conditions.

Hydrothermally stable, acid-resistant nickel catalysts are highly desired in hydrogenation reactions, but such a catalyst remains absent owing to the inherent vulnerability of nickel under acidic conditions. An ultra-durable Ni-N-C single-atom catalyst (SAC) has now been developed that possesses a remarkable Ni content (7.5 wt %) required for practical usage. This SAC shows not only high activities for hydrogenation of various unsaturated substrates but also unprecedented durability for the one-pot conversion of cellulose under very harsh conditions (245 °C, 60 bar H2 , presence of tungstic acid in hot water). Using integrated spectroscopy characterization and computational modeling, the active site structure is identified as (Ni-N4)⋅⋅⋅N, where significantly distorted octahedral coordination and pyridinic N constitute a frustrated Lewis pair for the heterolytic dissociation of dihydrogen, and the robust covalent chemical bonding between Ni and N atoms accounts for its ultrastability.

Effects of intravenous nicardipine followed by oral labetalol in combination with nifedipine controlled-release tablet on severe peripartum hypertension.

OBJECTIVES: To investigate the effects of intravenous nicardipine as initial therapy and oral labetalol combined with nifedipine controlled-release tablet as subsequent treatment of severe peripartum hypertension. MATERIAL AND METHODS: Intravenous nicardipine was delivered as the initial treatment, after the target blood pressure (BP) had been achieved, oral labetalol was used to maintain the target BP. If oral labetalol failed to maintain the target BP, oral labetalol combined with nifedipine controlled-release tablet was used. RESULTS: A total number of 131 patients were enrolled. The target BP (BP < 140/90 mmHg) was achieved in all patients within 60 minutes by intravenous nicardipine. After receiving labetalol orally, the target BP was maintained in nine patients. However, in 104 patients, we had to combine oral labetalol and nifedipine controlled-release tablet due to re-elevation of their systolic BP to 140-159 mmHg. In 18 patients, we restarted intravenous nicardipine because their systolic BP re-elevated above 160 mm Hg. Among the 104 patients who received oral labetalol and nifedipine controlled-release tablet, the target BP was achieved and maintained in 96 patients, and eight patients had to restart nicardipine. Of the total number of 26 patients in whom intravenous nicardipine was resumed, the target BP was successfully maintained in 22 patients with oral labetalol combined with nifedipine controlled-release tablet. CONCLUSIONS: Intravenous nicardipine rapidly and safely lowered severe peripartum hypertension. As subsequent therapy, oral labetalol combined with nifedipine controlled-release tablet protocol may be applied to effectively maintain a target BP.