Promote electroreduction of CO2 via catalyst valence state manipulation by surface-capping ligand.

Electrochemical CO2 reduction provides a potential means for synthesizing value-added chemicals over the near equilibrium potential regime, i.e., formate production on Pd-based catalysts. However, the activity of Pd catalysts has been largely plagued by the potential-depended deactivation pathways (e.g., [Formula: see text]-PdH to [Formula: see text]-PdH phase transition, CO poisoning), limiting the formate production to a narrow potential window of 0 V to -0.25 V vs. reversible hydrogen electrode (RHE). Herein, we discovered that the Pd surface capped with polyvinylpyrrolidone (PVP) ligand exhibits effective resistance to the potential-depended deactivations and can catalyze formate production at a much extended potential window (beyond -0.7 V vs. RHE) with significantly improved activity (~14-times enhancement at -0.4 V vs. RHE) compared to that of the pristine Pd surface. Combined results from physical and electrochemical characterizations, kinetic analysis, and first-principle simulations suggest that the PVP capping ligand can effectively stabilize the high-valence-state Pd species (Pdδ+) resulted from the catalyst synthesis and pretreatments, and these Pdδ+ species are responsible for the inhibited phase transition from [Formula: see text]-PdH to [Formula: see text]-PdH, and the suppression of CO and H2 formation. The present study confers a desired catalyst design principle, introducing positive charges into Pd-based electrocatalyst to enable efficient and stable CO2 to formate conversion.

Large scanning field laser concurrent drilling system with a five-axis independent control for special-shaped holes.

Five-axis laser scanning technology is an effective drilling method for special-shaped holes. Due to a gap in laser angle-of-incidence (AOI) control within a large scanning field, current technologies are challenging for fabricating large-size holes or special-shaped hole arrays. In this paper, a large scanning field five-axis laser concurrent drilling system was proposed. The laser AOI was independently controlled using two pairs of synchronous deflection mirrors. The laser control deviations under a large scanning field were investigated systematically by simulation and experiment. By establishing a complete correction method, the laser AOI control within a scanning field diameter of up to 35 mm was achieved. A series of special-shaped holes were fabricated concurrently on a 3.6 mm thick glass fiber reinforced plastic (GFRP), verifying that the AOI can be controlled by the five-axis laser scanning system. Our work provides a novel method to increase the scanning field of the five-axis laser scanning technology, expanding the application scope of the five-axis laser processing.

Estimating the CO2 emissions of Chinese cities from 2011 to 2020 based on SPNN-GNNWR.

Global warming is a serious threat to human survival and health. Facing increasing global warming, the issue of CO2 emissions has attracted more attention. China is a major contributor of anthropogenic CO2 emissions and so it is essential to accurately estimate China's CO2 emissions and analyze their changing characteristics. This study recalculates CO2 emissions from Chinese cities from 2011 to 2020 using the SPNN-GNNWR model and multiple factors to reduce the uncertainty in emission estimates. The SPNN-GNNWR model has excellent predictions (R2: 0.925, 10-fold CV R2: 0.822) when cross-validation is used. The results indicate that the total CO2 emissions in China calculated by the model are close to those accounted for by other authorities in the world, with the total CO2 emissions increasing from 9.122 billion tonnes in 2011 to 9.912 billion tonnes in 2020. The city with the largest increase in CO2 emissions is Tianjin, and the city with the largest decrease is Beijing. The study also reveals the regional differences in CO2 emissions in Chinese mainland, including emissions, emission intensity and per capita emissions. Capturing and understanding the emissions and the related socioeconomic characteristics of different cities can help to develop effective emission mitigation strategies.

Polyoxometalate Interlayered Zinc-Metallophthalocyanine Molecular Layer Sandwich as Photocoupled Electrocatalytic CO2 Reduction Catalyst.

Developing efficient and robust heterogeneous metallophthalocyanine electrocatalysts for CO2 reduction remains a challenge. Here, a general synthetic method of zinc-metallophthalocyanine (MPc) molecular layer/polyoxometalate (POM) sandwich lamellar material is developed, and thus improved performance of electrocatalytic and photocoupled electrocatalytic CO2 reduction is achieved. The incorporation of POM could prevent the packing of MPc molecular layers from aggregation, which would be favorable to the exposure of active sites. The molecular layer sandwich catalyst presents superior CO2 reduction activity, delivering the highest CO Faradaic efficiency (FECO) of 96.1% at -0.7 V vs RHE in dark field. Under light irradiation, over 93% FECO is achieved in a broad potential range from -0.6 to -0.9 V vs RHE with a maximum of 96.2%, and the carbon monoxide turnover frequency could exceed 2060 h-1. Photoelectrochemical tests and luminescence characterizations reveal the molecular layer is beneficial for carrier separation during light irradiation; density functional theory calculations and electron paramagnetic resonance indicated a 2-fold enhancement of the external light field on the catalytic performance.

POM-Incorporated CoO Nanowires for Enhanced Photocatalytic Syngas Production from CO2.

Utilizing sustainable energy for chemical activation of small molecules, such as CO2 , to produce important chemical feedstocks is highly desirable. The simultaneous production of CO/H2 mixture (syngas) from photoreduction of CO2 and H2 O is highly promising. However, the relationships between structure, composition, crystallinity, and photocatalytic performance are still indistinct. Here, amorphous ultrathin CoO nanowires and polyoxometalate incorporated nanowires with even lower crystallinity were synthesized. The POM-incorporated ultrathin nanowires exhibit high photocatalytic syngas production activity, reaching H2 and CO evolution rates of 11555 and 4165 µmol g-1 h-1 respectively. Further experiments indicate that the ultrathin morphology and incorporation of POM both contribute to the superior performance. Multiple characterizations reveal the enhanced charge-hole separation efficiency of the catalyst would facilitate the photocatalysis.

Freestanding Millimeter-Scale Porphyrin-Based Monoatomic Layers with 0.28†nm Thickness for CO2 Electrocatalysis.

Developing two-dimensional (2D) and single atomic layered materials is a fascinating challenge. Here we successfully synthesize porphyrin-based monoatomic layer (PML), a freestanding 2D porphyrin-based material of monomer-unit thickness (2.8 Å). The solvothermal method provides a bottom-up approach for tailoring the monoatomic layer from the nanoscale to the milliscale. PMLs containing accurately tailorable M-N4 units (M=Cu and Au) were synthesized, which present metal center-dependent performance for CO2 electrocatalysis. PML with Cu-N4 centers performs high faradaic efficiencies of HCOO- and CH4 (80.86 % and 11.51 % at -0.7 V, respectively) while PML with Au-N4 centers generates HCOO- and CO as major products (40.90 % and 34.40 % at -0.8 V, respectively). Irreversible restructuring behavior of Cu sites is also observed. Based on the graphene-like properties and metal center-selectivity relationships, we believe that PML will play a distinct role in various applications.

Nickel Diselenide Ultrathin Nanowires Decorated with Amorphous Nickel Oxide Nanoparticles for Enhanced Water Splitting Electrocatalysis.

Well-designed hybrid materials based on noble metal-free elements have great potential to generate hydrogen (H2 ) and oxygen (O2 ) sustainably via overall water splitting for developing practical energy-related technologies. Herein, an accessible method is presented to synthesize nickel diselenide (NiSe2 ) ultrathin nanowires decorated with amorphous nickel oxide nanoparticles (NiOx NPs) as multifunctional electrocatalysts (NSWANs) for hydrogen and oxygen evolution reaction (HER and OER). The NSWANs exhibit quite low HER and OER overpotentials of 174 and 295 mV, respectively, holding the current density of 20 mA cm-2 for 24 h continuous operations in alkaline media. Meanwhile, a cell voltage of 1.547 V at the current density of 10 mA cm-2 for overall water splitting has been achieved by the NSWANs for the practical application, which could maintain fascinating activity of 20 mA cm-2 for 72 h without degradation. The decorated NiOx NPs not only prevent the NiSe2 from further oxidation but also expose requisite active sites for electrocatalytic process. It is believed that this study may provide a valuable strategy to design high-efficiency electrocatalysts and expand the applications of selenide-based materials.

Enhancing Cu-ligand interaction for efficient CO2 reduction towards multi-carbon products.

Electrochemical CO2 reduction (CO2R) to valuable products provides a promising strategy to enable CO2 utilization sustainably. Here, we report the strategy of using Cu-DAT (3,5-diamino-1,2,4-triazole) as a catalyst precursor for efficient CO2 reduction, demonstrating over 80% selectivity towards multicarbon products at 400 mA cm-2, with intrinsic activity over 19 times higher than that of Cu nanoparticles. The catalyst's active phase is determined to be metallic copper wrapped with the DAT ligand. We attribute this enhanced CO2R performance to the accelerated steps of *CO adsorption and C-C coupling induced by the closely cooperated DAT ligand.

Revealing the structural evolution of CuAg composites during electrochemical carbon monoxide reduction.

Comprehending the catalyst structural evolution during the electrocatalytic process is crucial for establishing robust structure/performance correlations for future catalysts design. Herein, we interrogate the structural evolution of a promising Cu-Ag oxide catalyst precursor during electrochemical carbon monoxide reduction. By using extensive in situ and ex situ characterization techniques, we reveal that the homogenous oxide precursors undergo a transformation to a bimetallic composite consisting of small Ag nanoparticles enveloped by thin layers of amorphous Cu. We believe that the amorphous Cu layer with undercoordinated nature is responsible for the enhanced catalytic performance of the current catalyst composite. By tuning the Cu/Ag ratio in the oxide precursor, we find that increasing the Ag concentration greatly promotes liquid products formation while suppressing the byproduct hydrogen. CO2/CO co-feeding electrolysis and isotopic labelling experiments suggest that high CO concentrations in the feed favor the formation of multi-carbon products. Overall, we anticipate the insights obtained for Cu-Ag bimetallic systems for CO electroreduction in this study may guide future catalyst design with improved performance.

A pilot study of [68Ga]Ga-fibroblast activation protein inhibitor-04 PET/CT in renal cell carcinoma.

OBJECTIVES: As a promising positron emission tomography (PET) tracer, [68Ga]Ga-fibroblast activation protein inhibitor-04([68Ga]Ga-FAPI-04) performs better than 2-[18F]fluoro-2-deoxy-d-glucose ([18F]FDG) at diagnosing primary and metastatic lesions in patients with various types of cancer. We investigated the utility of [68Ga]Ga-FAPI-04 PET/CT for the detection of primary and metastatic lesions in renal cell carcinoma (RCC). [18F]FDG PET/CT were used for comparison. METHODS: Twenty-two patients with suspected RCC or recurrent RCC were enrolled in our study. Among these patients, 14 were newly diagnosed with RCC, 3 had recurrent RCC, and 5 were excluded from further analysis due to having benign renal tumours. Seventeen patients with RCC underwent [68Ga]Ga-FAPI-04 PET/CT, and 6 of them also received [18F]FDG PET/CT. The positive detection rates were calculated and compared with those in patients who underwent both scans. RESULTS: Data from 17 patients with RCC (median age: 60.5 years, interquartile range [IQR]: 54-70 years) were evaluated. The positive detection rate of [68Ga]Ga-FAPI-04 PET/CT for RCC was 64.7% (11/17). Lymph node metastases (n = 44), lung metastasis (n = 1), and bone metastasis (n = 1) were detected. Six patients with RCC underwent [68Ga]Ga-FAPI-04 and [18F]FDG PET/CT. [68Ga]Ga-FAPI-04 PET/CT showed a higher positive detection rate than [18F]FDG PET/CT in detecting RCC (83.3% [5/6] vs. 50% [3/6], P = 0.545). Additionally, [68Ga]Ga-FAPI-04 PET/CT has higher SUVmax (3.20 [IQR: 2.91-5.80 vs. 2.71 [IQR: 2.13-3.10], P = 0.116) and tumour-to-background ratio (TBR) values (1.60 [IQR: 1.33-3.67] vs. 0.86 [0.48-1.21], P = 0.028) than [18F]FDG PET/CT. CONCLUSIONS: These findings suggest that [68Ga]Ga-FAPI-04 PET/CT has potential value in RCC diagnosis. Further studies are warranted to validate these results. ADVANCES IN KNOWLEDGE: Clinical utility of [68Ga]Ga-FAPI-04 in RCC remains unclear, and there are not many similar studies in the literature. We evaluated the role of [68Ga]Ga-FAPI-04 in diagnosing RCC.

Climate and soil stressed elevation patterns of plant species to determine the aboveground biomass distributions in a valley-type Savanna.

Introduction: Extreme environments such as prolonged high temperatures and droughts can cause vulnerability of vegetation ecosystems. The dry-hot valleys of Southwestern China, known for their extremely high annual temperature, lack of water, and unique non-zonal "hot island" habitat in the global temperate zone, provide exceptional sites for studying how plant adapts to the prolonged dry and hot environment. However, the specific local biotic-environment relationships in these regions remain incompletely elucidated. The study aims to evaluate how valley-type Savanna vegetation species and their communities adapt to long-term drought and high-temperature stress environments. Methods: The study investigated the changes in species diversity and communities' aboveground biomass of a valley-type Savanna vegetation along an elevation gradient of Yuanmou dry-hot valley in Jinsha River basin, southwest China. Subsequently, a general linear model was utilized to simulate the distribution pattern of species diversities and their constituent biomass along the elevation gradient. Finally, the RDA and VPH mothed were used to evaluate the impacts and contributions of environmental factors or variables on the patterns. Results and discussion: The field survey reveals an altitudinal gradient effect on the valley-type Savanna, with a dominant species of shrubs and herbs plants distribution below an elevation of 1700m, and a significant positive relationship between the SR, Shannon-Wiener, Simpson, and Pielou indices and altitudes. Relatively, the community aboveground biomass did not increase significantly with elevation, which was mainly due to a decreased biomass of herbaceous plants along the elevation. Different regulators of shrub-herbaceous plant species and their functional groups made different elevation patterns of species diversity and aboveground biomass in valley-type Savannas. Herbaceous plants are responsible for maintaining species diversity and ensuring stability in the aboveground biomass of the vegetation. However, the influence of shrubs on aboveground biomass became more pronounced as environmental conditions varied along the altitudinal gradient. Furthermore, species diversity was mainly influenced by soil and climatic environmental factors, whereas community biomass was mainly regulated by plant species or functional groups. The study demonstrates that the spatial pattern of valley-type Savanna was formed as a result of different environmental responses and the productive capacity of retained plant species or functional groups to climate-soil factors, highlighting the value of the Yuanmou dry-hot Valley as a microcosm for exploring the intricate interactions between vegetation evolution and changes in environmental factors.

Directing oxygen reduction reaction selectivity towards hydrogen peroxide via electric double layer engineering.

The electrochemical oxygen reduction reaction (ORR) has been recognized as a promising alternative for the sustainable production of H2O2. Here, we report a facile and effective strategy to promote ORR selectivity towards the 2e- product H2O2via electric double layer engineering. Specifically, in a model system using immobilized cobalt phthalocyanine as the electrocatalyst, H2O2 selectivity has been improved from below 60% to over 93%, and the intrinsic activity for H2O2 formation has been enhanced by more than 3 times upon the introduction of a cationic surfactant (i.e., cetyltrimethylammonium bromide, CTAB) into the electrolyte. Based on detailed kinetics analysis, we conclude that the accelerated H2O2 formation rate results from the reduced charge transfer resistance in the rate limiting step and the promoted oxygen uptake rate. We propose that the electric field strength across the electric double layer is enhanced via the self-assembled single-tail cationic surfactant layer at the electrode/electrolyte interface, which is the origin of the enhancement of the 2e- ORR performance.

Diversity of platinum-sites at platinum/fullerene interface accelerates alkaline hydrogen evolution.

Membrane-based alkaline water electrolyser is promising for cost-effective green hydrogen production. One of its key technological obstacles is the development of active catalyst-materials for alkaline hydrogen-evolution-reaction (HER). Here, we show that the activity of platinum towards alkaline HER can be significantly enhanced by anchoring platinum-clusters onto two-dimensional fullerene nanosheets. The unusually large lattice distance (~0.8 nm) of the fullerene nanosheets and the ultra-small size of the platinum-clusters (~2 nm) leads to strong confinement of platinum clusters accompanied by pronounced charge redistributions at the intimate platinum/fullerene interface. As a result, the platinum-fullerene composite exhibits 12 times higher intrinsic activity for alkaline HER than the state-of-the-art platinum/carbon black catalyst. Detailed kinetic and computational investigations revealed the origin of the enhanced activity to be the diverse binding properties of the platinum-sites at the interface of platinum/fullerene, which generates highly active sites for all elementary steps in alkaline HER, particularly the sluggish Volmer step. Furthermore, encouraging energy efficiency of 74% and stability were achieved for alkaline water electrolyser assembled using platinum-fullerene composite under industrially relevant testing conditions.

Low androgen status inhibits erectile function by upregulating the expression of proteins of mitochondria-associated membranes in rat corpus cavernosum.

OBJECTIVE: To investigate the effect of low androgen status on mitochondria-associated membranes (MAMs) and its relationship with erectile function. METHODS: A total of 36 eight-week-old male Sprague-Dawley rats were randomly divided into six groups: the control (sham-operated) group, the castration group, the castration + testosterone (cast + T) group, the control + siRNA group, the cast + siRNA group, and the cast + empty vector group. Testosterone propionate (3 mg/kg) was subcutaneously injected into the rats in the cast + T group every other day starting from the second day after the surgery. Four weeks later, lentiviral vectors carrying phosphofurin acidic cluster sorting protein 2 (PACS-2) gene-specific siRNA (1 × 108 TU/ml, 10 µl) were injected into the rats in the siRNA groups. At the sixth week of castration, the ratio of the maximum intracavernous pressure/the mean arterial pressure (ICPmax/MAP), the levels of nitric oxide (NO), endothelial nitric oxide synthase (eNOS), phospho-eNOS (p-eNOS), fatty acid-CoA ligase 4 (FACL-4), PACS-2, and inositol 1,4,5-trisphosphate receptor type 1 (IP3R1) in the penile corpus cavernosum were determined. RESULTS: The FACL-4, PACS-2, and IP3R1 were primarily localized in the cytoplasm of endothelial cells and part of smooth muscle cells in the corpus cavernosum. The level of NO, the ratio of ICPmax/MAP, and p-eNOS/eNOS were decreased significantly in the castration group compared with the control group (p < 0.01). The expressions of FACL-4, PACS-2, and IP3R1 were increased significantly in the castration group compared with the control group (p < 0.01). The level of NO, the ratios of ICPmax/MAP, and the ratio of p-eNOS/eNOS were increased significantly in the cast + siRNA group compared with the castration group (p < 0.01). The expressions of FACL-4 and PACS-2 were decreased significantly in the cast + siRNA group compared with the castration group (p < 0.01). CONCLUSION: Low androgen status upregulated the expressions of patients in MAMs (FACL-4, PACS-2, and IP3R1) in the corpus cavernosum and inhibited the eNOS/NO/cGMP signaling pathway, resulting in impaired erectile function in rats. Erectile function may be improved by inhibiting the high expression of PACS-2 in the corpus cavernosum under low androgen state.

Tailoring Layer Number of 2D Porphyrin-Based MOFs Towards Photocoupled Electroreduction of CO2.

Inspired by the success of graphene, a series of single- or few-layer 2D materials have been developed and applied in the past decade. Here, the successful preparation of monolayer and bilayer 2D porphyrin-based metal-organic frameworks (MOFs) by a facile solvothermal method is reported. The structure transition from monolayer to bilayer drives distinct electronic properties and restructuring behaviors, which finally results in distinct catalytic pathways towards CO2 electrocatalysis. The monolayer favors CO2 -to-C2 pathway due to the restructuring of CuO4 sites, while CO and HCOO- are the major products over the bilayer. In photocoupled electrocatalysis, the Faradaic efficiency (FE) of the C2 compounds shows a nearly fourfold increase on the monolayer than that under dark conditions (FEC2 increases from 11.9% to 41.1% at -1.4 V). For comparison, the light field plays a negligible effect on the bilayer. The light-induced selectivity optimization is investigated by experimental characterization and density functional theory (DFT) calculations. This work opens up a novel possibility to tune the selectivity of carbon products just by tailoring the layer number of the 2D material.

Boosting CO2 Electroreduction via the Synergistic Effect of Tuning Cationic Clusters and Visible-Light Irradiation.

Introducing an external light field can increase the intrinsic activity and energy efficiency for electrochemical CO2 reduction. Herein, a synergistic strategy that introduces photosensitive components and visible light into a stable system is reported to improve the performance for CO2 reduction. The catalytic kinetics studies indicate that the synergistic effect of implantation of cationic Ti and additional light driving is the primary responsibility for accelerating the first electron transfer to form a *COO- intermediate. This leads to a satisfactory CO2 -to-CO conversion for Zr/Ti-NB-Co in terms of high selectivity (Faradaic efficiency of 93.6% at -0.7 V), remarkable catalytic activity (production rate up to 546 mmol g-1 h-1 at -1.1 V), excellent long-term stability (without performance decay over 11 h), and large turnover frequency of 1028 h-1 at -1.1 V under visible light. These results imply that the photodriven Ti-based porphyrin catalyst not only can deliver more electrons, but also can act as a photoswitch to adjust the electron transfer pathway.

Enhancing CO2 Electrocatalysis on 2D Porphyrin-Based Metal-Organic Framework Nanosheets Coupled with Visible-Light.

2D catalysts combined with single atom sites are promising candidates to promote CO2 reduction performance, but the ability to target stable materials with distinct structure still remains challenging. Herein, a series of single metal atoms anchored 2D metal-organic framework nanosheets (MOF-NS-M) with visualized and well-ordered mesoporous structures are fabricated and exhibit enhanced CO2 reduction activity and selectivity with the assistance of visible-light. Encouragingly, the CO Faradaic efficiency of MOF-NS-Co exceeds 90% in a wide potential window of -0.5 to -1.0 V versus RHE and reaches 98.7% with 100 mV positive shift compared with the result measured under dark. The catalytic kinetics studies show a fast initial electron transfer to CO2 to form *COO- , thanks to the sufficient exposed active sites resulting from the nanosheet nature and adjusted electron transfer pathway caused by the porphyrin photoswitch.

Nanoconfined Water-Molecule Channels for High-Yield Solar Vapor Generation under Weaker Sunlight.

Solar vapor generation is a promising method to efficiently produce fresh water. However, the insufficient vapor yields under natural daylight restrict its practical applications, and the basic evaporation mechanisms are deficient for reasonable design of evaporator structure. Here, hydrophobic nano-confined water molecule channels (NCWMCs) are demonstrated, which can reduce the vaporization enthalpy for water evaporation and achieve a record vapor generation rate of 1.25 kg m-2 h-1 under 0.5 sun irradiation. Molecular dynamics simulations reveal the cluster-evaporation process in the NCWMC system. As a result, the evaporator with NCWMC system can effectively purify seawater and wastewater samples using this environmentally friendly strategy.

Secondary-Component Incorporated Hollow MOFs and Derivatives for Catalytic and Energy-Related Applications.

Their highly functional nature has endowed metal-organic frameworks (MOFs) with diverse applications. On this basis, a higher demand has been proposed for the preparation of novel-structured MOFs. Hollow MOFs have been intensively studied and exhibited versatile properties, and among the various methods, secondary-component incorporation has been proved promising in the design and preparation of complex structures with requisite properties. Herein, the synthesis and applications of secondary component incorporated MOFs and their derivatives are systematically reviewed. Two main methodologies, preincorporation and postmodification, are discussed in detail, and the role of the secondary component is demonstrated. Based on these introductions, the applications of those materials, including chemical catalysis, electrocatalysis, and energy storage applications, are summarized. Finally, a personal outlook for the future opportunities and challenges in this field is given.

2-Methylimidazole assisted ultrafast synthesis of carboxylate-based metal-organic framework nano-structures in aqueous medium at room temperature.

Carboxylate-based metal-organic frameworks (CMOFs) have received considerable attentions for their high stability, catalytic activity, and porosity. However, synthesis of CMOFs requires high temperature, pressure, and long reaction time. Here, we explored the activity of 2-methylimidazole (2-MIM) for ultrafast synthesis of CMOF nanostructures (CMOFNs), in aqueous medium at room temperature and reaction time of 10 min. Seven CMOFNs have been synthesized by using Al3+, Cr3+, Cu2+, Fe3+, In3+, or Cd2+ salt and 1,4-bezenedicarboxylic acid, or 1,3,5-benzenetricarboxylic acid. Through this technique, the CMOFs with space time yield 181-501 kg m-3 day-1 and crystal sizes of ca. 200-700 nm was obtained.