Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 µmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

A Janus Platinum/Tin Oxide Heterostructure for Durable Oxygen Reduction Reaction.

Designing efficient and durable electrocatalysts for oxygen reduction reaction (ORR) is essential for proton exchange membrane fuel cells (PEMFCs). Platinum-based catalysts are considered efficient ORR catalysts due to their high activity. However, the degradation of Pt species leads to poor durability of catalysts, limiting their applications in PEMFCs. Herein, a Janus heterostructure is designed for high durability ORR in acidic media. The Janus heterostructure composes of crystalline platinum and cassiterite tin oxide nanoparticles with carbon support (J-Pt@SnO2/C). Based on the synchrotron fine structure analysis and electrochemical investigation, the crystalline reconstruction and charge redistribution at the interface of Janus structure are revealed. The tightly coupled interface could optimize the valance states of Pt and the adsorption/desorption of oxygenated intermediates. As a result, the J-Pt@SnO2/C catalyst possesses distinguishing long-term stability during the accelerated durability test without obvious degradation after 40 000 cycles and keeps the majority of activity after 70 000 cycles. Meanwhile, the catalyst exhibits outstanding activity with half-wave potential at 0.905 V and a mass activity of 0.355 A mgPt -1 (2.7 times higher than Pt/C). The approach of the Janus catalyst paves an avenue for designing highly efficient and stable Pt-based ORR catalyst in the future implementation.

Prediction of cerebral infarction after bypass surgery in adult moyamoya disease: using pulsatility index on TCD.

BACKGROUND: At present, the most effective treatment for symptomatic moyamoya disease (MMD) is surgery. However, the high incidence of postoperative complications is a serious problem plaguing the surgical treatment of MMD, especially the acute cerebral infarction. Decreased cerebrovascular reserve is an independent risk factor for ischemic infarction, and the pulsatility index (PI) of transcranial Doppler (TCD) is a common intuitive index for evaluating intracranial vascular compliance. However, the relationship between PI and the occurrence of ischemic stroke after operation is unclear. OBJECTIVE: To explore whether the PI in the middle cerebral artery (MCA) could serve as a potential predictor for the occurrence of ischemic infarction after bypass surgery in MMD. METHODS: We performed a retrospective analysis of data from 71 patients who underwent combined revascularization surgery, including superficial temporal artery-middle cerebral artery (STA-MCA) anastomosis and encephalo-duro-myo-synangiosis (EDMS). The patients were divided into two groups according to the median of ipsilateral MCA-PI before operation, low PI group (MCA-PI < 0.614) and high PI group (MCA-PI ≥ 0.614). Univariate and multivariate regression analysis were used to explore risk factors affecting the occurrence of postoperative cerebral infarction. RESULTS: Among the 71 patients with moyamoya disease, 11 patients had cerebral infarction within one week after revascularization. Among them, 10 patients' ipsilateral MCA-PI were less than 0.614, and another one's MCA- PI is higher than 0.614. Univariate analysis showed that the lower ipsilateral MCA-PI (0.448 ± 0.109 vs. 0.637 ± 0.124; P = 0.001) and higher Suzuki stage (P = 0.025) were linked to postoperative cerebral infarction. Multivariate analysis revealed that lower ipsilateral MCA-PI was an independent risk factor for predicting postoperative cerebral infarction (adjusted OR = 14.063; 95% CI = 6.265 ~ 37.308; P = 0.009). CONCLUSIONS: A lower PI in the ipsilateral MCA may predict the cerebral infarction after combined revascularization surgery with high specificity. And combined revascularization appears to be safer for the moyamoya patients in early stages.

Remote Synergy between Heterogeneous Single Atoms and Clusters for Enhanced Oxygen Evolution.

Integrating single atoms and clusters into one system is a novel strategy to achieve desired catalytic performances. Compared with homogeneous single-atom cluster catalysts, heterogeneous ones combine the merits of different species and therefore show greater potential. However, it is still challenging to construct single-atom cluster systems of heterogeneous species, and the underlying mechanism for activity improvement remains unclear. In this work, we developed a heterogeneous single-atom cluster catalyst (ConIr1/N-C) for efficient oxygen evolution. The Ir single atoms worked in synergy with the Co clusters at a distance of about 8 Å, which optimized the configuration of the key intermediates. Consequently, the oxygen evolution activity was significantly improved on ConIr1/N-C relative to the Co cluster catalyst (Con/N-C), exhibiting an overpotential lower by 107 mV than that of Con/N-C at 10 mA cm-2 and a turnover frequency 50.9 times as much as that of Con/N-C at an overpotential of 300 mV.

Neighbouring Synergy in High-Density Single Ir Atoms on CoGaOOH for Efficient Alkaline Electrocatalytic Oxygen Evolution.

The catalytic performance of single-atom catalysts was strictly limited by isolated single-atom sites. Fabricating high-density single atoms to realize the synergetic interaction in neighbouring single atoms could optimize the adsorption behaviors of reaction intermediates, which exhibited great potential to break performance limitations and deepen mechanistic understanding of electrocatalysis. However, the catalytic behavior governed by neighbouring single atoms is particularly elusive and has yet to be understood. Herein, we revealed that the synergetic interaction in neighbouring single atoms contributes to superior performance for oxygen evolution relative to isolated Ir single atoms. Neighbouring single atoms was achieved by fabricating high-density single atoms to narrow the distance between single atoms. Electrochemical measurements demonstrated that the Nei-Ir1/CoGaOOH with neighbouring Ir single atoms exhibited a low overpotential of 170 mV at a current density of 10 mA cm-2, and long-durable stability over 2000 h for oxygen evolution. Mechanistic studies revealed that neighbouring single atoms synergetic stabilized the *OOH intermediates via extra hydrogen bonding interactions, thus significantly reducing the reaction energy barriers, as compared to isolated Ir single atoms. The discovery of the synergetic interaction in neighbouring single atoms could offer guidance for the development of efficient electrocatalysts, thus accelerating the world's transition to sustainable energy.

Regulating Spin States in Oxygen Electrocatalysis.

Developing efficient and stable transition metal oxides catalysts for energy conversion processes such as oxygen evolution reaction and oxygen reduction reaction is one of the key measures to solve the problem of energy shortage. The spin state of transition metal oxides is strongly correlated with their catalytic activities. In an octahedral structure of transition metal oxides, the spin state of active centers could be regulated by adjusting the splitting energy and the electron pairing energy. Regulating spin state of active centers could directly modulate the d orbitals occupancy, which influence the strength of metal-ligand bonds and the adsorption behavior of the intermediates. In this review, we clarified the significance of regulating spin state of the active centers. Subsequently, we discussed several characterization technologies for spin state and some recent strategies to regulate the spin state of the active centers. Finally, we put forward some views on the future research direction of this vital field.

Tuning the Electronic and Steric Interaction at the Atomic Interface for Enhanced Oxygen Evolution.

The two-dimensional surface or one-dimensional interface of heterogeneous catalysts is essential to determine the adsorption strengths and configurations of the reaction intermediates for desired activities. Recently, the development of single-atom catalysts has enabled an atomic-level understanding of catalytic processes. However, it remains obscure whether the conventional concept and mechanism of one-dimensional interface are applicable to zero-dimensional single atoms. In this work, we arranged the locations of single atoms to explore their interfacial interactions for improved oxygen evolution. When iridium single atoms were confined into the lattice of CoOOH, efficient electron transfer between Ir and Co tuned the adsorption strength of oxygenated intermediates. In contrast, atomic iridium species anchored on the surface of CoOOH induced inappreciable modification in electronic structures, whereas steric interactions with key intermediates at its Ir-OH-Co interface played a primary role in reducing its energy barrier toward oxygen evolution.

Fe-N complex biochar as a superior partner of sodium sulfide for methyl orange decolorization by combination of adsorption and reduction.

To enhance the decolorization of methyl orange (MO), Fe-N complex biochar (Fe-N-BC) was developed as an accelerator in the sodium sulfide (Na2S) reduction system. The decolorization effect and mechanism of MO in the Fe-N-BC/Na2S composite system were studied. Surface pore analysis, Raman spectroscopy, FT-IR, XPS, and electrochemical analysis were used to characterize Fe-N-BC and unmodified biochar (BC). These results demonstrated that Fe-N-BC had better adsorption performance (specific surface area 463.46 m2 g-1) and electron transfer capacity than BC. By adding Fe-N-BC to the Na2S reduction system for MO, it was found that the decolorization of MO was greatly improved (increased by 93%). Besides, the effects of critical factors such as the initial concentration of Na2S, the dosage of Fe-N-BC, pH value, and temperature on the decolorization rate of MO were evaluated. Through the analysis of the action mechanism, the cooperation mode of Fe-N-BC and Na2S was to form an infinite cycle of adsorption-reduction-regeneration, so as to realize the rapid decolorization of MO. On the one hand, Fe-N-BC could adsorb MO and Na2S on its surface to increase the contact opportunity; on the other hand, it could act as a redox mediator to accelerate the electron transfer of the reduction reaction. In addition, the degradation of MO by Na2S was also an in-situ regeneration of Fe-N-BC. These findings may provide a feasible method to decolorize azo dyes quickly by cooperating with chemical reducing agents from a new perspective.

Surface engineering-based S, N co-doped biochar for improved anaerobic digestion: Enhancing microbial-pollutant and inter-microbial electron transfer synergistic EPS protection.

Enhancing extracellular electron transfer (EET) efficiency is crucial for improving the anaerobic digestion (AD) system's capability to treat recalcitrant wastewater. In this study, a novel S, N co-doped biochar (S-N-BC) was prepared through surface engineering to optimize EET within AD systems. The addition of S-N-BC significantly enhanced the performance of a mesophilic AD system treating Congo red wastewater, increasing the decolorization rate by 78 %, COD degradation rate by 82 %, and methane yield by 87 % compared to the control. Additionally, the shock resistance of anaerobic granular sludge was improved, as evidenced by the formation of the protective extracellular polymeric substances (EPS) barrier and the enhanced activities of the electron transport system. Mechanistic analysis revealed that adding S-N-BC did not alter the Congo red decolorization pathway but significantly enriched various electrochemically active bacteria and established EET pathways between microbial-pollutant and inter-microbial. This significantly accelerated EET efficiency within the AD system, ensuring stable and efficient operation under challenging conditions. This study proposed a novel approach using S-N-BC to simultaneously enhance "dual-pathway EET" between microbial-pollutant and inter-microbial while constructing an EPS protective barrier, addressing the issues of low efficiency and fragile stability of AD systems for treating recalcitrant wastewater.

Elucidating microbial iron corrosion mechanisms with a hydrogenase-deficient strain of Desulfovibrio vulgaris.

Sulfate-reducing microorganisms extensively contribute to the corrosion of ferrous metal infrastructure. There is substantial debate over their corrosion mechanisms. We investigated Fe0 corrosion with Desulfovibrio vulgaris, the sulfate reducer most often employed in corrosion studies. Cultures were grown with both lactate and Fe0 as potential electron donors to replicate the common environmental condition in which organic substrates help fuel the growth of corrosive microbes. Fe0 was corroded in cultures of a D. vulgaris hydrogenase-deficient mutant with the 1:1 correspondence between Fe0 loss and H2 accumulation expected for Fe0 oxidation coupled to H+ reduction to H2. This result and the extent of sulfate reduction indicated that D. vulgaris was not capable of direct Fe0-to-microbe electron transfer even though it was provided with a supplementary energy source in the presence of abundant ferrous sulfide. Corrosion in the hydrogenase-deficient mutant cultures was greater than in sterile controls, demonstrating that H2 removal was not necessary for the enhanced corrosion observed in the presence of microbes. The parental H2-consuming strain corroded more Fe0 than the mutant strain, which could be attributed to H2 oxidation coupled to sulfate reduction, producing sulfide that further stimulated Fe0 oxidation. The results suggest that H2 consumption is not necessary for microbially enhanced corrosion, but H2 oxidation can indirectly promote corrosion by increasing sulfide generation from sulfate reduction. The finding that D. vulgaris was incapable of direct electron uptake from Fe0 reaffirms that direct metal-to-microbe electron transfer has yet to be rigorously described in sulfate-reducing microbes.

Synergistic enhancement of microbes-to-pollutants and inter-microbes electron transfer by Fe, N modified ordered mesoporous biochar in anaerobic digestion.

Extracellular electron transfer was essential for degrading recalcitrant pollutants by anaerobic digestion (AD). Therefore, existing studies improved AD efficiency by enhancing the electron transfer from microbes-to-pollutants or inter-microbes. This study synthesized a novel Fe, N co-doped biochar (Fe, N-BC), which could enhance both the microbes-to-pollutants and inter-microbes electron transfer in AD. Detailed characterization data indicated that Fe, N-BC has an ordered mesoporous structure, high specific surface area (463.46 m2/g), and abundant redox functional groups (Fe2+/Fe3+, pyrrolic-N), which translate into excellent biocompatibility and electrochemical properties of Fe, N-BC. By adding Fe, N-BC, the stability and efficiency of the medium-temperature AD system in the treatment of methyl orange (MO) wastewater were improved: obtained a high degradation efficiency of MO (96.8 %) and enhanced the methane (CH4) production by 65 % compared to the control group. Meanwhile, Fe, N-BC reduced the accumulation of volatile fatty acids in the AD system, and the activity of anaerobic granular sludge electron transport system and coenzyme F420 was enhanced. In addition, Fe, N-BC showed positive enrichment of azo dyes decolorization bacteria (Georgenia) and direct interspecies electron transfer (DIET) synergistic partners (Syntrophobacter, Methanosarcina). Overall, the rapid degradation of MO and enhanced CH4 production in AD systems by Fe, N-BC is associated with enhancing two electronic pathways, i.e., microbes to MO and DIET between syntrophic bacteria and methanogenic archaea. This study introduced an enhanced "two-pathways of electron transfer" theory, realized by Fe, N-BC. These findings provided new insights into the interactions within AD systems and offer strategies for enhancing their performance with recalcitrant pollutants.

Zirconium Doping to Enable High-Efficiency and Stable CsPbI2Br All-Inorganic Perovskite Solar Cells.

All-inorganic wide-bandgap perovskite CsPbI2Br has attracted much attention because of its inherent thermal stability and ideal bandgap for the front subcell of tandem solar cells (TSCs). However, the low power conversion efficiency (PCE) and poor moisture stability of CsPbI2Br still restrict its future commercialization. Herein, zirconium tetrachloride (ZrCl4) was doped into CsPbI2Br films to modulate the crystal growth and improve the film quality. The partial substitution of the B-site Pb2+ of CsPbI2Br with Zr4+ suppresses the unwanted phase conversion from the crystallized black α-phase to the δ-phase, resulting in improved phase stability. Consequently, the humidity and thermal stability of the film are greatly improved. Additionally, the incorporation of ZrCl4 suppresses nonradiative recombination and forms a matched energy-level alignment with the hole-transport layer (Spiro-OMeTAD). Benefiting from these features, the ZrCl4-doped CsPbI2Br perovskite solar cell (PSC) shows an outstanding efficiency of 16.60% with a high open-circuit voltage of 1.29 V. The unencapsulated devices simultaneously show excellent humidity and thermal stability, retaining over 91% of PCEinitial after 1000 h of aging in ambient air conditions and 92% PCEinitial after 500 h of continuous heating at 85 °C in a nitrogen environment, respectively. Furthermore, ZrCl4-doped CsPbI2Br was employed as the front subcell of perovskite/organic TSCs and achieved a remarkable PCE of 19.42%, showing great potential for highly efficient and stable TSCs.

Halogen-Functionalized Hole Transport Materials with Strong Passivation Effects for Stable and Highly Efficient Quasi-2D Perovskite Solar Cells.

The performance of quasi-two-dimensional (Q-2D) perovskite solar cells (PSCs) strongly depends on the interface characteristics between the hole transport material (HTM) and the perovskite layer. In this work, we designed and synthesized a series of HTMs with triphenylamine-carbazole as the core structure and modified end groups with chlorine and bromine atoms. These HTMs show deeper highest occupied molecular orbital energy levels than commercial HTMs. This reduced energy band mismatch between the HTM and perovskite layer facilitates efficient charge extraction at the interface. Moreover, these HTMs containing halogen atoms on the end groups could form halogen bonding with the Pb2+ ions at the buried interface of the perovskite layer, effectively passivating defects to suppress nonradiative recombination. Additionally, halogen bonding also contributes to the formation of vertically oriented perovskite crystals with a high quality. By incorporation of chlorohexane-substituted HTMs, the resultant Q-2D PSCs exhibited the highest power conversion efficiency of 21.07%. Furthermore, the devices show improved stability, retaining 97.2% of their initial efficiency after 1100 h of continuous illumination.

Distance effect of single atoms on stability of cobalt oxide catalysts for acidic oxygen evolution.

Developing efficient and economical electrocatalysts for acidic oxygen evolution reaction (OER) is essential for proton exchange membrane water electrolyzers (PEMWE). Cobalt oxides are considered promising non-precious OER catalysts due to their high activities. However, the severe dissolution of Co atoms in acid media leads to the collapse of crystal structure, which impedes their application in PEMWE. Here, we report that introducing acid-resistant Ir single atoms into the lattice of spinel cobalt oxides can significantly suppress the Co dissolution and keep them highly stable during the acidic OER process. Combining theoretical and experimental studies, we reveal that the stabilizing effect induced by Ir heteroatoms exhibits a strong dependence on the distance of adjacent Ir single atoms, where the OER stability of cobalt oxides continuously improves with decreasing the distance. When the distance reduces to about 0.6 nm, the spinel cobalt oxides present no obvious degradation over a 60-h stability test for acidic OER, suggesting potential for practical applications.

Universal Formation of Single Atoms from Molten Salt for Facilitating Selective CO2 Reduction.

Clarifying the formation mechanism of single-atom sites guides the design of emerging single-atom catalysts (SACs) and facilitates the identification of the active sites at atomic scale. Herein, a molten-salt atomization strategy is developed for synthesizing zinc (Zn) SACs with temperature universality from 400 to 1000/1100 °C and an evolved coordination from Zn-N2Cl2 to Zn-N4. The electrochemical tests and in situ attenuated total reflectance-surface-enhanced infrared absorption spectroscopy confirm that the Zn-N4 atomic sites are active for electrochemical carbon dioxide (CO2) conversion to carbon monoxide (CO). In a strongly acidic medium (0.2 m K2SO4, pH = 1), the Zn SAC formed at 1000 °C (Zn1NC) containing Zn-N4 sites enables highly selective CO2 electroreduction to CO, with nearly 100% selectivity toward CO product in a wide current density range of 100-600 mA cm-2. During a 50 h continuous electrolysis at the industrial current density of 200 mA cm-2, Zn1NC achieves Faradaic efficiencies greater than 95% for CO product. The work presents a temperature-universal formation of single-atom sites, which provides a novel platform for unraveling the active sites in Zn SACs for CO2 electroreduction and extends the synthesis of SACs with controllable coordination sites.

The efficacy of STA-MCA double anastomosis comparing to single anastomosis in chronic internal carotid artery occlusion patients.

OBJECTIVE: To investigate the efficacy of STA-MCA double-anastomosis and single-anastomosis in patients with cerebral hypoperfusion caused by chronic internal carotid artery occlusion(CICAO). METHODS: In this retrospective study, data were collected from 19 patients with CICAO who underwent STA-MCA anastomosis at our hospital between January 2016 and January 2022, and they were divided into single anastomosis group and double anastomosis group according to the surgical method. The study collected general clinical data from both groups, including age, sex, lipid levels, blood pressure, glucose levels, smoking and alcohol consumption. Additionally, pre- and postoperative neurological function, cerebral hemodynamic parameters, and postoperative ischemic events were also recorded. By combining our study findings with the existing literature, a comparative analysis of the efficacy of single- and double-anastomosis in patients with CICAO was conducted. RESULTS: Prior to surgical treatment，there were no statistically significant differences in cerebral hemodynamic parameters, including rob (0.65 ± 0.09 VS. 0.62 ± 0.04), rut (1.73 ± 0.40 VS. 1.99 ± 0.53), and rTMax (2.02 ± 0.49 VS. 1.72 ± 0.46), as well as neurofunctional scores, including modified Rankin Scale (MRS) (2.8 ± 1.03 VS. 2.4 ± 0.88) and National Institutes of Health Stroke Scale (NIHSS) (9.1 ± 5.08 VS. 8.3 ± 4.09) between the two groups. After operation, rCBF (single: 0.65 ± 0.09 VS.0.84 ± 0.08, p = 0.007; double: 0.62 ± 0.04 VS.1.08 ± 0.20, p = 0.001) were significantly increased in both groups, but the rMTT (1.99 ± 0.53 VS.1.27 ± 0.42, p = 0.0447) and rTMax (1.72 ± 0.46 VS.1.16 ± 0.16, p = 0.038) showed significant differences postoperatively only in the double-anastomosis group. The MRS (single: 1.8 ± 1.23, double: 1.7 ± 0.9) in both groups and the NIHSS (7.2 ± 5.11) in single-anastomosis group were not improved after surgery, while the NIHSS (8.3 ± 4.09 VS.4.4 ± 3.08, p = 0.037) in double-anastomosis group was improve significantly. In summary, the double-anastomosis group showed better improvement in rCBF and NIHSS scores compared to the single-anastomosis group.(ΔrCBF: 0.19±0.09 VS. 0.45±0.18, p=0.02, ΔNIHSS: 1.9±0.56 VS. 4±1.73, p=0.002). The cases were followed up for 20.3 ± 18.6 months, and there were no ischemic events in either group during the follow-up period. CONCLUSION: STA-MCA revascularization can improve CBF in patients with hypoperfusion caused by CICAO, and prevent the reoccurrence of ischemic stroke effectively. Compared with single-anastomosis, double-anastomosis can provide more CBF and improve neurologic dysfunction.