Vacancy-enabled N2 activation for ammonia synthesis on an Ni-loaded catalyst.

Ammonia (NH3) is pivotal to the fertilizer industry and one of the most commonly produced chemicals1. The direct use of atmospheric nitrogen (N2) had been challenging, owing to its large bond energy (945 kilojoules per mole)2,3, until the development of the Haber-Bosch process. Subsequently, many strategies have been explored to reduce the activation barrier of the N≡N bond and make the process more efficient. These include using alkali and alkaline earth metal oxides as promoters to boost the performance of traditional iron- and ruthenium-based catalysts4-6 via electron transfer from the promoters to the antibonding bonds of N2 through transition metals7,8. An electride support further lowers the activation barrier because its low work function and high electron density enhance electron transfer to transition metals9,10. This strategy has facilitated ammonia synthesis from N2 dissociation11 and enabled catalytic operation under mild conditions; however, it requires the use of ruthenium, which is expensive. Alternatively, it has been shown that nitrides containing surface nitrogen vacancies can activate N2 (refs. 12-15). Here we report that nickel-loaded lanthanum nitride (LaN) enables stable and highly efficient ammonia synthesis, owing to a dual-site mechanism that avoids commonly encountered scaling relations. Kinetic and isotope-labelling experiments, as well as density functional theory calculations, confirm that nitrogen vacancies are generated on LaN with low formation energy, and efficiently bind and activate N2. In addition, the nickel metal loaded onto the nitride dissociates H2. The use of distinct sites for activating the two reactants, and the synergy between them, results in the nickel-loaded LaN catalyst exhibiting an activity that far exceeds that of more conventional cobalt- and nickel-based catalysts, and that is comparable to that of ruthenium-based catalysts. Our results illustrate the potential of using vacancy sites in reaction cycles, and introduce a design concept for catalysts for ammonia synthesis, using naturally abundant elements.

The spontaneous symmetry breaking in Ta2NiSe5 is structural in nature.

The excitonic insulator is an electronically driven phase of matter that emerges upon the spontaneous formation and Bose condensation of excitons. Detecting this exotic order in candidate materials is a subject of paramount importance, as the size of the excitonic gap in the band structure establishes the potential of this collective state for superfluid energy transport. However, the identification of this phase in real solids is hindered by the coexistence of a structural order parameter with the same symmetry as the excitonic order. Only a few materials are currently believed to host a dominant excitonic phase, Ta2NiSe5 being the most promising. Here, we test this scenario by using an ultrashort laser pulse to quench the broken-symmetry phase of this transition metal chalcogenide. Tracking the dynamics of the material's electronic and crystal structure after light excitation reveals spectroscopic fingerprints that are compatible only with a primary order parameter of phononic nature. We rationalize our findings through state-of-the-art calculations, confirming that the structural order accounts for most of the gap opening. Our results suggest that the spontaneous symmetry breaking in Ta2NiSe5 is mostly of structural character, hampering the possibility to realize quasi-dissipationless energy transport.

Dipole Coupling Accelerated H2 O Dissociation by Magnesium-Based Intermetallic Catalysts.

The water (H2 O) dissociation is critical for various H2 O-associated reactions, including water gas shift, hydrogen evolution reaction and hydrolysis corrosion. While the d-band center concept offers a catalyst design guideline for H2 O activation, it cannot be applied to intermetallic or main group elements-based systems because Coulomb interaction was not considered. Herein, using hydrolysis corrosion of Mg as an example, we illustrate the critical role of the dipole of the intermetallic catalysts for H2 O dissociation. The H2 O dissociation kinetics can be enhanced using Mgx Mey (Me=Co, Ni, Cu, Si and Al) as catalysts, and the hydrogen generation rate of Mg2 Ni-loaded Mg reached 80 times as high as Ni-loaded Mg. The adsorbed H2 O molecules strongly couple with the Mg-Me dipole of Mgx Mey , lowering the H2 O dissociation barrier. The dipole-based H2 O dissociation mechanism is applicable to non-transition metal-based systems, such as Mg2 Si and Mg17 Al12 , offering a flexible catalyst design strategy for controllable H2 O dissociation.

Boosted Activity of Cobalt Catalysts for Ammonia Synthesis with BaAl2O4-xHy Electrides.

Electrides are promising support materials to promote transition metal catalysts for ammonia synthesis due to their strong electron-donating ability. Cobalt (Co) is an alternative non-noble metal catalyst to ruthenium in ammonia synthesis; however, it is difficult to achieve acceptable activity at low temperatures due to the weak Co-N interaction. Here, we report a novel oxyhydride electride, BaAl2O4-xHy, that can significantly promote ammonia synthesis over Co (500 mmol gCo-1 h-1 at 340 °C and 0.90 MPa) with a very low activation energy (49.6 kJ mol-1; 260-360 °C), which outperforms the state-of-the-art Co-based catalysts, being comparable to the latest Ru catalyst at 300 °C. BaAl2O4-xHy with a stuffed tridymite structure has interstitial cage sites where anionic electrons are accommodated. The surface of BaAl2O4-xHy with very low work functions (1.7-2.6 eV) can donate electrons strongly to Co, which largely facilitates N2 reduction into ammonia with the aid of the lattice H- ions. The stuffed tridymite structure of BaAl2O4-xHy with a three-dimensional AlO4-based tetrahedral framework has great chemical stability and protects the accommodated electrons and H- ions from oxidation, leading to robustness toward the ambient atmosphere and good reusability, which is a significant advantage over the reported hydride-based catalysts.

Rationally Integrating 2D Confinement and High Sodiophilicity toward SnO2 /Ti3 C2 Tx Composites for High-Performance Sodium-Metal Anodes.

The metallic sodium (Na) is characterized by high theoretical specific capacity, low electrode potential and abundant resources, and its advantages manifests itself as a promising candidate anode of sodium metal batteries (SMBs). However, the vaporization during the plating/stripping or uncontrolled growth of sodium dendrites in sodium metal anodes (SMAs) has posed major challenges to its practical applications. To address this issue, here, the SnO2 /Ti3 C2 Tx composite is rationally fabricated, in which sodiophilic SnO2 nanoparticles are in situ dispersed on the 2D Ti3 C2 Tx , providing the acceptor sites of Na+  that can control vaporization and dendrites. The SnO2 /Ti3 C2 Tx composite anode exhibits smooth and homogeneous morphology after Na-metal deposition cycles, stable Coulombic efficiency (CE) of half cells, long stable cycles of symmetric cells due to highly sodiophilic sites, and confinement effect. In addition, the full cells assembled with Na0.6 MnO2 also show excellent rate performance and cycling performance. These discoveries demonstrate the effectiveness of the acceptor sites and the confinement effect provided by the SnO2 /Ti3 C2 Tx composite, and thus provide an additional degree of freedom for designing SMBs.

Unconventional excitonic states with phonon sidebands in layered silicon diphosphide.

Complex correlated states emerging from many-body interactions between quasiparticles (electrons, excitons and phonons) are at the core of condensed matter physics and material science. In low-dimensional materials, quantum confinement affects the electronic, and subsequently, optical properties for these correlated states. Here, by combining photoluminescence, optical reflection measurements and ab initio theoretical calculations, we demonstrate an unconventional excitonic state and its bound phonon sideband in layered silicon diphosphide (SiP2), where the bound electron-hole pair is composed of electrons confined within one-dimensional phosphorus-phosphorus chains and holes extended in two-dimensional SiP2 layers. The excitonic state and emergent phonon sideband show linear dichroism and large energy redshifts with increasing temperature. Our ab initio many-body calculations confirm that the observed phonon sideband results from the correlated interaction between excitons and optical phonons. With these results, we propose layered SiP2 as a platform for the study of excitonic physics and many-particle effects.

Intermetallic Copper-Based Electride Catalyst with High Activity for C-H Oxidation and Cycloaddition of CO2 into Epoxides.

Inorganic electrides have been proved to be efficient hosts for incorporating transition metals, which can effectively act as active sites giving an outstanding catalytic performance. Here, it is demonstrated that a reusable and recyclable (for more than 7 times) copper-based intermetallic electride catalyst (LaCu0.67 Si1.33 ), in which the Cu sites activated by anionic electrons with low-work function are uniformly dispersed in the lattice framework, shows vast potential for the selective C-H oxidation of industrially important hydrocarbons and cycloaddition of CO2 with epoxide. This leads to the production of value-added cyclic carbonates under mild reaction conditions. Importantly, the LaCu0.67 Si1.33 catalyst enables much higher turnover frequencies for the C-H oxidation (up to 25 276 h-1 ) and cycloaddition of CO2 into epoxide (up to 800 000 h-1 ), thus exceeding most nonnoble as well as noble metal catalysts. Density functional theory investigations have revealed that the LaCu0.67 Si1.33 catalyst is involved in the conversion of N-hydroxyphthalimide (NHPI) into the phthalimido-N-oxyl (PINO), which then triggers selective abstraction of an H atom from ethylbenzene for the generation of a radical susceptible to further oxygenation in the presence of O2 .

Anomalous Size Effect of Pt Ultrathin Nanowires on Oxygen Reduction Reaction.

The classical size effect of Pt particles on oxygen reduction reaction (ORR) suggests that the activity and durability would decrease with reducing the particle size, self-limiting the effectiveness in maximizing the Pt utilization efficiency with the particle-size-reduction strategy. Herein, we discover an anomalous size effect based on Pt nanowires (NWs) with tunable diameters, where the monotonically increasing activity and durability for ORR were observed with decreasing the diameter from 2.4 to 1.1 nm. Our results reveal that the dominant role of increased compressive strain induced by decreasing the diameter of NWs in weakening the adsorption and suppressing the Pt dissolution accounts for this anomalous size effect, where the reduced low-coordinated sites on NWs, the intrinsic structural advantage, is the root. Our findings not only expand the knowledge to the classical size effect but also provide new implications to break through the size limit in the design of Pt-based ORR catalysts.

A Label-Free Fluorescence Aptasensor Based on G-Quadruplex/Thioflavin T Complex for the Detection of Trypsin.

A novel, label-free fluorescent assay has been developed for the detection of trypsin by using thioflavin T as a fluorescent probe. A specific DNA aptamer can be combined by adding cytochrome c. Trypsin hydrolyzes the cytochrome c into small peptide fragments, exposing the G-quadruplex part of DNA aptamer, which has a high affinity for thioflavin T, which then enhances the fluorescence intensity. In the absence of trypsin, the fluorescence intensity was inhibited as the combination of cytochrome c and the DNA aptamer impeded thioflavin T's binding. Thus, the fluorescent biosensor showed a linear relationship from 0.2 to 60 µg/mL with a detection limit of 0.2 µg/mL. Furthermore, the proposed method was also successfully employed for determining trypsin in biological samples. This method is simple, rapid, cheap, and selective and possesses great potential for the detection of trypsin in bioanalytical and biological samples and medical diagnoses.

Approach to Chemically Durable Nickel and Cobalt Lanthanum-Nitride-Based Catalysts for Ammonia Synthesis.

Metal nitride complexes have recently been proposed as an efficient noble-metal-free catalyst for ammonia synthesis utilizing a dual active site concept. However, their high sensitivity to air and moisture has restricted potential applications. We report that their chemical sensitivity can be improved by introducing Al into the LaN lattice, thereby forming La-Al metallic bonds (La-Al-N). The catalytic activity and mechanism of the resulting TM/La-Al-N (TM=Ni, Co) are comparable to the previously reported TM/LaN catalyst. Notably, the catalytic activity did not degrade after exposure to air and moisture. Kinetic analysis and isotopic experiment showed that La-Al-N is responsible for N2 absorption and activation despite substantial Al being introduced into its lattice because the local coordination of the lattice N remained largely unchanged. These findings show the effectiveness of metallic bond formation, which can support the chemical stability of rare-earth nitrides with retention of catalytic functionality.

Dissociative and Associative Concerted Mechanism for Ammonia Synthesis over Co-Based Catalyst.

The current catalytic reaction mechanism for ammonia synthesis relies on either dissociative or associative routes, in which adsorbed N2 dissociates directly or is hydrogenated step-by-step until it is broken upon the release of NH3 through associative adsorption. Here, we propose a concerted mechanism of associative and dissociative routes for ammonia synthesis over a cobalt-loaded nitride catalyst. Isotope exchange experiments reveal that the adsorbed N2 can be activated on both Co metal and the nitride support, which leads to superior low-temperature catalytic performance. The cooperation of the surface low work function (2.6 eV) feature and the formation of surface nitrogen vacancies on the CeN support gives rise to a dual pathway for N2 activation with much reduced activation energy (45 kJ·mol-1) over that of Co-based catalysts reported so far, which results in efficient ammonia synthesis under mild conditions.

Peripheral blood circulating microRNA-4636/-143 for the prognosis of cervical cancer.

Cervical cancer is the third leading cause of female death in the world. Serum microRNAs (miRNAs) are currently considered to be valuable as noninvasive cancer biomarkers, but their role in the prognosis of cervical cancer has not been elucidated. We aimed to find serum miRNAs that can be used as prognostic factors for cervical cancer. A traumatic pathological biopsy is the only reliable method for determining the severity of cervical cancer currently. Thus, noninvasive diagnostic markers are needed. The serological expression of candidate miRNAs were measured in 90 participants, including 60 patients with cervical cancer and 50 patients with cervical intraepithelial neoplasia. Two patients with cervical cancer were excluded from the study because of lack of data. miRNAs were evaluated by quantitative reverse transcription polymerase chain reaction. miR-143/-4636 appeared specific for cervical cancer compared with cervical intraepithelial neoplasia (P < .001). The classification performance of validated miRNAs for cervical cancer [Area under the receiver operating characteristic curve (AUC) = 0.942] was better than that reached by squamous cell carcinoma antigen (SCC-Ag; AUC = 0.727). Poor-differentiation group has lower miR-143/-4636 levels in serum (P < .05). miR-4636 level was correlated gross tumor volume and the depth of invasion (P < .0001). In our study, we found a combination of miR-143 and miR-4636 that is independently and strongly associated with cervical cancer prognosis and can be used as a clinically prognostic factor.

Contribution of Nitrogen Vacancies to Ammonia Synthesis over Metal Nitride Catalysts.

Ammonia is one of the most important feedstocks for the production of fertilizer and as a potential energy carrier. Nitride compounds such as LaN have recently attracted considerable attention due to their nitrogen vacancy sites that can activate N2 for ammonia synthesis. Here, we propose a general rule for the design of nitride-based catalysts for ammonia synthesis, in which the nitrogen vacancy formation energy (ENV) dominates the catalytic performance. The relatively low ENV (ca. 1.3 eV) of CeN means it can serve as an efficient and stable catalyst upon Ni loading. The catalytic activity of Ni/CeN reached 6.5 mmol·g-1·h-1 with an effluent NH3 concentration (ENH3) of 0.45 vol %, reaching the thermodynamic equilibrium (ENH3 = 0.45 vol %) at 400 °C and 0.1 MPa, thereby circumventing the bottleneck for N2 activation on Ni metal with an extremely weak nitrogen binding energy. The activity far exceeds those for other Co- and Ni-based catalysts, and is even comparable to those for Ru-based catalysts. It was determined that CeN itself can produce ammonia without Ni-loading at almost the same activation energy. Kinetic analysis and isotope experiments combined with density functional theory (DFT) calculations indicate that the nitrogen vacancies in CeN can activate both N2 and H2 during the reaction, which accounts for the much higher catalytic performance than other reported nonloaded catalysts for ammonia synthesis.

X-box binding protein l splicing attenuates brain microvascular endothelial cell damage induced by oxygen-glucose deprivation through the activation of phosphoinositide 3-kinase/protein kinase B, extracellular signal-regulated kinases, and hypoxia-inducible factor-1α/vascular endothelial growth factor signaling pathways.

Angiogenesis is positively correlated with the survival rate of stroke patients. Therefore, studying factors that initiate and promote angiogenesis after ischemic stroke is crucial for finding novel and effective treatment targets that improve the prognosis of stroke. X-box binding protein l splicing (XBP1s) plays a positive regulatory role in cell proliferation and angiogenesis. However, the role and mechanism of XBP1s on the proliferation of brain microvascular endothelial cells (BMECs) and angiogenesis after cerebral ischemia remains unclear. In the current study, we investigated the role XBP1s plays in BMEC proliferation and angiogenesis following cerebral ischemia. In this study, the roles of XBP1s on cell survival, apoptosis, cycle migration, and angiogenesis were determined in oxygen-glucose deprivation (OGD) treated BMECs. The expression of XBP1s in BMECs, which were exposed to OGD at 0, 2, 4, and 6 hr, increased in a time-dependent manner. The overexpression of XBP1s promoted cell survival, cell cycle, migration, and angiogenesis of BMECs, and inhibited the apoptosis in OGD-treated BMECs. In addition, the overexpression of XBP1s promoted the expression of cyclin D1, matrix metalloproteinase (MMP-2), and MMP-9, but inhibited cleaved Caspase-3 and cleaved Caspase-9 expression in OGD-treated BMECs. The overexpression of XBP1s also promoted the expression of hypoxia-inducible factor 1-alpha, vascular endothelial growth factor, phosphatidylinositol-4,5-bisphosphate 3-kinase, p-AKT, p-mTOR, p-GSK3ß, and p-extracellular signal-regulated kinase1/2 in OGD-treated BMECs. The effect of XBP1s silencing was opposite to that of XBP1s overexpression. In conclusion, using an in vitro OGD model, we demonstrated that XBP1s may be a promising target for ischemic stroke therapy to maintain BMECs survival and induce angiogenesis.

Unconventional p-d Hybridization Interaction in PtGa Ultrathin Nanowires Boosts Oxygen Reduction Electrocatalysis.

Alloying 3d transition metals with Pt has been discovered as an effective strategy to boost the catalytic activity in oxygen reduction reaction (ORR), which, however, often raises the insufficient catalyst durability issue due to rapid leaching of the 3d metal elements. To overcome this issue and realize enhancements in both the activity and the durability properties, here we report a new catalytic structure based on PtGa ultrathin alloy nanowires (NWs), which feature an unconventional strong p-d hybridization interaction. Relative to commercial Pt catalyst, the optimum Pt4.31Ga NWs catalyst exhibited 10.5- and 12.1-fold enhancement in the ORR mass activity and specific activity, respectively. Particularly, the Pt4.31Ga NWs catalyst showed only 15.8% loss in the mass activity after 30 000 cycles of durability test, as compared to a big decrease of 79.6% for the commercial Pt catalyst. Our mechanistic studies find a strong p-d hybridization interaction between Ga and Pt that accounts for the improved ORR performance via synergistically optimizing the surface electronic structure, enhancing the oxidation resistance of Pt, and suppressing the leaching of lattice Ga. We believe this work provides new perspectives to design active and durable electrocatalysts toward ORR.

Hollowsphere Nanoheterojunction of g-C3N4@TiO2 with High Visible Light Photocatalytic Property.

In this work, g-C3N4@TiO2 nanostructures with hollow sphere morphology, small grain size, high crystalline quality, and high surface area are successfully synthesized by the annealing method using melamine and hollowsphere precursor, which could be a universal method to synthesis hollow sphere nanoheterojunction. Excellent photocatalytic property was observed from the as-prepared g-C3N4@TiO2 nanostructure with 466.43 µmol·g-1·h-1 hydrogen generation rate under visible light irradiation (>420 nm), which was 5.5 times as much as the control couple, nanoparticle nanoheterojunction g-C3N4@TiO2. No apparent deactivation was found during the follow-up cycle performance test. The special morphology and the heterojunction construction contribute to both visible light absorption and photogenerated electron-hole pair separation efficiency and finally to the photocatalytic property. The content of g-C3N4 was proved to be an important parameter for the promotion of the photocatalytic property. Overlarge content may lead to lower photogenerated electron-hole pair separation efficiency.

Pseudogap Control of Physical and Chemical Properties in CeFeSi-Type Intermetallics.

We describe the synthesis of the new ternary compound CaRuSi whose chemical and physical properties help draw a clear picture of how electronic structure controls the behavior of an isostructural series of intermetallics. DFT calculations reveal that an electronic pseudogap arises near the Fermi level ( EF), corresponding to 14 valence electrons per RuSi unit. The closed-shell-like character is further investigated by comparisons with the electronic structures of CaCoSi (15 electrons), where the EF lies above the corresponding pseudogap, and its hydride CaCoSiH, where formation of H anions restores the 14-electron count on the metal sublattice, returning the EF to the pseudogap. The chemical origin of the 14-electron pseudogap is interpreted with a reversed approximation Molecular Orbital analysis. Here, the pseudogap is shown to coincide with the filling of Ru 16 electron configurations isolobal to the d8 square planar complexes of coordination chemistry (but where 4 electron pairs are shared covalently between Ru atoms such that only 12 electrons are required), and the occupation of Si lone pairs (2 electrons). Experimentally, the pseudogap is confirmed with heat capacity measurements, which indicate that the 14-electron systems CaRuSi and CaCoSiH each exhibit  a smaller electronic density of states at the EF than the 15-electron system CaCoSi. Importantly, the 14-electron pseudogap also significantly affects the chemical properties of the compounds, as evidenced by the difference in the stabilities of CaCoSiH and CaRuSiH observed in hydrogen desorption measurements. These results may support the design of functional materials for superconductivity, hydrogen storage, and catalysis involving hydrogenation.

Cu2O photocathodes for unassisted solar water-splitting devices enabled by noble-metal cocatalysts simultaneously as hydrogen evolution catalysts and protection layers.

Here, we report a Cu2O-based photocathode applied with pulsed-laser-deposited overlayers with the structure of Ga2O3/AZO/TiO2 and 60 nm dense Pt simultaneously as a hydrogen evolution catalyst and protective layer under backside illumination from ITO substrate. And by depositing thin Au nanoparticles on the bottom of Cu2O, we observe the increase of light harvesting and the production of hot electrons from the surface plasmon resonance effect. The modified photocathode presents a photocurrent density of -4 mA cm-2 at 0 V versus reversible hydrogen electrode and a thermodynamically-based energy conversion efficiency of 0.27% in a weak acidic electrolyte. The stability is tremendously improved compared with other structures without the dense Pt layer. This enhancement is attributed to the formation of a p-n junction at the Cu2O and Ga2O3 interface and surface stabilization by TiO2 and Pt. To demonstrate the impact on the practical application of the photocathode, we fabricate the bias-free solar water-splitting tandem device using a transparent BiVO4 photoanode, which exhibits a stabilized peak photocurrent density of 0.1 mA cm-2 under continuous illumination.