Surface-Integrating Oxygen Vacancy and CuxO Nanodots Enabling Synergistic Electric Field and Dual Catalytic Sites Boosting CO2 Photoreduction.

High carrier separation efficiency and rapid surface catalytic reaction are crucial for enhancing catalytic CO2 photoreduction reaction. Herein, integrated surface decoration strategy with oxygen vacancies (Ov) and anchoring CuxO (1 < x < 2) nanodots below 10 nm is realized on Bi2MoO6 for promoting CO2 photoreduction performance. The charge interaction between Ov and anchored CuxO enables the formation of enhanced internal electric field, which provides a strong driving force for accelerating the separation of photocharge carriers on the surface of Bi2MoO6 (ηsurf ≈71%). They can also cooperatively reduce the surface work function of Bi2MoO6, facilitating the migration of carrier to the surface. Meanwhile, surface-integrated Ov and CuxO nanodots allowing dual catalytic sites strengthens the adsorption and activation CO2 into *CO2 over Bi2MoO6, considerably boosting the progression of CO2 conversion process. In the absence of co-catalyst or sacrificial agent, Bi2MoO6 with Ov and CuxO nanodots achieves a photocatalytic CO generation rate of 12.75 µmol g-1 h-1, a remarkable increase of over ≈15 times that of the original counterpart. This work provides a new idea for governing charge movement behaviors and catalytic reaction thermodynamics on the basis of synergistic improvement of electric field and active sites by coupling of the internal defects and external species.

Bipolaronic Motifs Induced Spatially Separated Catalytic Sites for Tunable Syngas Photosynthesis From CO2.

Photocatalytic reduction of CO2 into syngas is a promising way to tackle the energy and environmental challenges; however, it remains a challenge to achieve reaction decoupling of CO2 reduction and water splitting. Therefore, efficient production of syngas with a suitable CO/H2 ratio for Fischer-Tropsch synthesis can hardly be achieved. Herein, bipolaronic motifs including Co(II)-pyridine N motifs and Co(II)-imine N motifs are rationally designed into a crystalline imine-linked 1,10-phenanthroline-5,6-dione-based covalent organic framework (bp-Co-COF) with a triazine core. These featured structures with spatially separated active sites exhibit efficient photocatalytic performance toward CO2-to-syngas conversion with a suitable CO/H2 ratio (1:1-1:3). The bipolaronic motifs enable a highly separated electron-hole state, whereby the Co(II)-pyridine N motifs tend to be the active sites for CO2 activation and accelerate the hydrogenation to form *COOH intermediates; whilst, the Co(II)-imine N motifs increase surface hydrophilicity for H2 evolution. The photocatalytic reductions of CO2 and H2O thus decouple and proceed via a concerted way on the bipolaronic motifs of bp-Co-COF. The optimal bp-Co-COF photocatalyst achieves a high syngas evolution rate of 15.8 mmol g-1 h-1 with CO/H2 ratio of 1:2, outperforming previously reported COF-based photocatalysts.

Novel Angiogenesis Role of GLP-1(32-36) to Rescue Diabetic Ischemic Lower Limbs via GLP-1R-Dependent Glycolysis in Mice.

BACKGROUND: Restoring the capacity of endothelial progenitor cells (EPCs) to promote angiogenesis is the major therapeutic strategy of diabetic peripheral artery disease. The aim of this study was to investigate the effects of GLP-1 (glucagon-like peptide 1; 32-36)-an end product of GLP-1-on angiogenesis of EPCs and T1DM (type 1 diabetes) mice, as well as its interaction with the classical GLP-1R (GLP-1 receptor) pathway and its effect on mitochondrial metabolism. METHODS: In in vivo experiments, we conducted streptozocin-induced type 1 diabetic mice as a murine model of unilateral hind limb ischemia to examine the therapeutic potential of GLP-1(32-36) on angiogenesis. We also generated Glp1r-/- mice to detect whether GLP-1R is required for angiogenic function of GLP-1(32-36). In in vitro experiments, EPCs isolated from the mouse bone marrow and human umbilical cord blood samples were used to detect GLP-1(32-36)-mediated angiogenic capability under high glucose treatment. RESULTS: We demonstrated that GLP-1(32-36) did not affect insulin secretion but could significantly rescue angiogenic function and blood perfusion in ischemic limb of streptozocin-induced T1DM mice, a function similar to its parental GLP-1. We also found that GLP-1(32-36) promotes angiogenesis in EPCs exposed to high glucose. Specifically, GLP-1(32-36) has a causal role in improving fragile mitochondrial function and metabolism via the GLP-1R-mediated pathway. We further demonstrated that GLP-1(32-36) rescued diabetic ischemic lower limbs by activating the GLP-1R-dependent eNOS (endothelial NO synthase)/cGMP/PKG (protein kinase G) pathway. CONCLUSIONS: Our study provides a novel mechanism with which GLP-1(32-36) acts in modulating metabolic reprogramming toward glycolytic flux in partnership with GLP-1R for improved angiogenesis in high glucose-exposed EPCs and T1DM murine models. We propose that GLP-1(32-36) could be used as a monotherapy or add-on therapy with existing treatments for peripheral artery disease. REGISTRATION: URL: www.ebi.ac.uk/metabolights/; Unique identifier: MTBLS9543.

Increasing the Accessibility of Internal Catalytic Sites in Covalent Organic Frameworks by Introducing a Bicontinuous Mesostructure.

Introducing continuous mesochannels into covalent organic frameworks (COFs) to increase the accessibility of their inner active sites has remained a major challenge. Here, we report the synthesis of COFs with an ordered bicontinuous mesostructure, via a block copolymer self-assembly-guided nanocasting strategy. Three different mesostructured COFs are synthesized, including two covalent triazine frameworks and one vinylene-linked COF. The new materials are endowed with a hierarchical meso/microporous architecture, in which the mesochannels exhibit an ordered shifted double diamond (SDD) topology. The hierarchically porous structure can enable efficient hole-electron separation and smooth mass transport to the deep internal of the COFs and consequently high accessibility of their active catalytic sites. Benefiting from this hierarchical structure, these COFs exhibit excellent performance in visible-light-driven catalytic NO removal with a high conversion percentage of up to 51.4 %, placing them one of the top reported NO-elimination photocatalysts. This study represents the first case of introducing a bicontinuous structure into COFs, which opens a new avenue for the synthesis of hierarchically porous COFs and for increasing the utilization degree of their internal active sites.

Photocatalytic aerobic oxidation of C(sp3)-H bonds.

In modern industries, the aerobic oxidation of C(sp3)-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O2 and oxidation of C(sp3)-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp3)-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat-1) is observed. In addition to the direct oxidation of C(sp3)-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications.

A highly proton conductive perfluorinated covalent triazine framework via low-temperature synthesis.

Proton-conducting materials are essential to the emerging hydrogen economy. Covalent triazine frameworks (CTFs) are promising proton-conducting materials at high temperatures but need more effective sites to strengthen interaction for proton carriers. However, their construction and design in a concise condition are still challenges. Herein, we show a low temperature approach to synthesize CTFs via a direct cyclotrimerization of aromatic aldehyde using ammonium iodide as facile nitrogen source. Among the CTFs, the perfluorinated CTF (CTF-TF) was successfully synthesized with much lower temperature ( ≤ 160 °C) and open-air atmosphere. Due to the additional hydrogen-bonding interaction between fluorine atoms and proton carriers (H3PO4), the CTF-TF achieves a proton conductivity of 1.82 × 10-1 S cm-1 at 150 °C after H3PO4 loading. Moreover, the CTF-TF can be readily integrated into mixed matrix membranes, displaying high proton conduction abilities and good mechanical strength. This work provides an alternative strategy for rational design of proton conducting media.

Photo-Driven Quasi-Topological Transformation Exposing Highly Active Nitrogen Cation Sites for Enhanced Photocatalytic H2 O2 Production.

Herein, the exposure of highly-active nitrogen cation sites has been accomplished by photo-driven quasi-topological transformation of a 1,10-phenanthroline-5,6-dione-based covalent organic framework (COF), which contributes to hydrogen peroxide (H2 O2 ) synthesis during the 2-electron O2 photoreduction. The exposed nitrogen cation sites with photo-enhanced Lewis acidity not only act as the electron-transfer motor to adjust the inherent charge distribution, powering continuous and stable charge separation, and broadening visible-light adsorption, but also providing a large number of active sites for O2 adsorption. The optimal catalyst shows a high H2 O2 production rate of 11965 µmol g-1 h-1 under visible light irradiation and a remarkable apparent quantum yield of 12.9 % at 400 nm, better than most of the previously reported COF photocatalysts. This work provides new insights for designing photo-switchable nitrogen cation sites as catalytic centers toward efficient solar to chemical energy conversion.

Boosted C-C coupling with Cu-Ag alloy sub-nanoclusters for CO2-to-C2H4 photosynthesis.

The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C-C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu-Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 µmol g-1 h-1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu-Ag ASNCs, which enable an excellent C-C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C-C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.

Charge Density Modulation of Pyrene-Related Small Molecules by Nitrogen Heteroatoms Precisely Regulates Photocatalytic Generation of Hydrogen.

Organic semiconductor materials hold promising applications in photocatalytic hydrogen evolution due to their high modifiability and wide range of light absorption capability. In this study, we present an effective strategy for promoting the separation of photoexcited electrons from organic conjugated centers to active sites by modifying different nitrogen-containing groups on pyrene molecules. Building on this foundation, the well-designed catalyst Py-m-2N has demonstrated good performance by achieving a photocatalytic hydrogen evolution rate of 48.86 mmol g-1 h-1, even in the absence of the precious metal platinum cocatalyst. This achievement places the pyrene-based photocatalyst ahead of the majority of its organic counterparts. Our comprehensive characterization and density functional theory calculations reveal that the nitrogen atom not only serves as an active site for hydrogen production but also plays a pivotal role in efficiently accumulating bulk-phase electrons. This electron enrichment process enhances the transport of photoexcited electrons from the light-absorbing pyrene units to the active nitrogen sites. This work provides inspiration for the future design of effective nitrogen-atom-modified organic semiconductor photocatalysts at the molecular level.

Lipidomics Profiling Reveals Serum Phospholipids Associated with Albuminuria in Early Type 2 Diabetic Kidney Disease.

Early screening and administration of DKD are beneficial for renal outcomes of type 2 diabetic patients. However, the current early diagnosis using the albuminuria/creatine ratio (ACR) contains limitations. This study aimed to compare serum lipidome variation between type 2 diabetes and early DKD patients with increased albuminuria through an untargeted lipidomics method to explore the potential lipid biomarkers for DKD identification. 92 type 2 diabetic patients were enrolled and divided into two groups: DM group (ACR < 3 mg/mmol, n = 49) and early DKD group (3 mg/mmol ≤ ACR < 30 mg/mmol, n = 43). Fasting serum was analyzed through an ultraperformance liquid mass spectrometry tandem chromatography system (LC-MS). Orthogonal partial least-squares discriminant analysis (OPLS-DA) and univariate and multivariate analysis were performed to filter differentially depressed lipids. Receiver operating characteristic (ROC) curves were used to estimate the diagnostic capability of potential lipid biomarkers. We found that serum phospholipids including phosphatidylserine (PS), sphingomyelin (SM), and phosphatidylcholine (PC) were significantly upregulated in the DKD group and were highly correlated with the ACR. In addition, a panel of two phospholipids including PS(27:0)-H and PS(30:2e)-H showed good performance to help clinical lipids in early DKD identification, which increased the area under the curve (AUC) from 0.568 to 0.954. The study exhibited the serum lipidome variation in early DKD patients, and the increased phospholipids might participate in the development of albuminuria. The panel of PS(27:0)-H and PS(30:2e)-H could be a potential biomarker for DKD diagnosis.

INITIATION TIMING OF VASOPRESSOR IN PATIENTS WITH SEPTIC SHOCK: A SYSTEMATIC REVIEW AND META-ANALYSIS.

ABSTRACT: Background: Vasopressor plays a crucial role in septic shock. However, the time for vasopressor initiation remains controversial. We conducted a systematic review and meta-analysis to explore its initiation timing for septic shock patients. Methods: PubMed, Cochrane Library, Embase, and Web of Sciences were searched from inception to July 12, 2023, for relevant studies. Primary outcome was short-term mortality. Meta-analysis was performed using Stata 15.0. Results: Twenty-three studies were assessed, including 2 randomized controlled trials and 21 cohort studies. The early group resulted in lower short-term mortality than the late group (OR [95% CI] = 0.775 [0.673 to 0.893], P = 0.000, I2 = 67.8%). The significance existed in the norepinephrine and vasopressin in subgroup analysis. No significant difference was considered in the association between each hour's vasopressor delay and mortality (OR [95% CI] = 1.02 [0.99 to 1.051], P = 0.195, I2 = 57.5%). The early group had an earlier achievement of target MAP ( P < 0.001), shorter vasopressor use duration ( P < 0.001), lower serum lactate level at 24 h ( P = 0.003), lower incidence of kidney injury ( P = 0.001), renal replacement therapy use ( P = 0.022), and longer ventilation-free days to 28 days ( P < 0.001). Conclusions: Early initiation of vasopressor (1-6 h within septic shock onset) would be more beneficial to septic shock patients. The conclusion needs to be further validated by more well-designed randomized controlled trials.

ELABELA/APJ Axis Prevents Diabetic Glomerular Endothelial Injury by Regulating AMPK/NLRP3 Pathway.

ELABELA (ELA), a recently discovered peptide, is highly expressed in adult kidneys and the endothelium system. It has been identified as a novel endogenous ligand for the apelin receptor (APJ). This study aims to investigate the role of ELA in diabetic glomerular endothelial pyroptosis and its underlying mechanism. Initially, a significant decrease in ELA mRNA levels was observed in the renal cortex of db/db mice and high glucose-treated glomerular endothelial cells (GECs). It was also found that ELA deficiency in ELA+/- mice significantly accelerated diabetic glomerular injury, as shown by exacerbated glomerular morphological damage, increased serum creatine and blood urea nitrogen, and elevated 24-h urinary albumin excretion. In addition, in vivo overexpression of ELA prevented diabetic glomerular injury, reduced von Willebrand factor expression, restored endothelial marker CD31 expression, and attenuated the production of adhesive molecules such as intercellular adhesion molecule-1 and vascular cell adhesion molecule-1. Furthermore, in vitro studies confirmed that treatment with ELA inhibited GEC injury by regulating the NOD-like receptor protein 3 (NLRP3) inflammasome, as indicated by blocking NLRP3 inflammasome formation, decreasing cleaved Caspase-1 production, and inhibiting interleukin-1ß and interleukin-18 production. Moreover, in vitro experiments demonstrated that the protective effects of ELA in GECs during hyperglycemia were diminished by inhibiting adenosine monophosphate-activated protein kinase (AMPK) using Compound C or by APJ deficiency. Taken together, this study provides the first evidence that ELA treatment could prevent diabetic glomerular endothelial injury, which is partly mediated by the regulation of the AMPK/NLRP3 signaling pathway. Therefore, pharmacologically targeting ELA may serve as a novel therapeutic strategy for diabetic kidney disease.

Efficient photosynthesis of hydrogen peroxide by triazole-modified covalent triazine framework nanosheets.

Two-dimensional (2D) polymeric semiconductors, especially covalent triazine framework (CTF) nanosheets with aromatic triazine linkages are emerging as attractive metal-free photocatalysts owing to their predictable structures, good semiconducting properties, and high stability. However, the quantum size effect and ineffective electron screening of 2D CTF nanosheets cause an enlargement of electronic band gap and high excited electron-hole binding energies, which lead to low-level enhancements in photocatalytic performance. Herein, we present a novel triazole groups functionalized CTF nanosheet (CTF-LTZ) synthesized by facile combination of ionothermal polymerization and freeze-drying strategy from the unique letrozole precursor. The incorporation of the high-nitrogen-containing triazole group effectively modulates the optical and electronic properties, resulting in narrowed bandgap from 2.92 eV for unfunctionalized CTF to 2.22 eV for CTF-LTZ and dramatically improved charge separation, as well as highly-active sites for O2 adsorption. As a result, CTF-LTZ photocatalyst exhibits excellent performance and superior stability in H2O2 photosynthesis, with a high H2O2 production rate of 4068 µmol h-1 g-1 and a remarkable apparent quantum efficiency of 4.5 % at 400 nm. This work provides a simple and effective approach for rational design highly-efficient polymeric photocatalysts for H2O2 production.

Nanoarchitectonics of Metallene Materials for Electrocatalysis.

Controlling the synthesis of metal nanostructures is one approach for catalyst engineering and performance optimization in electrocatalysis. As an emerging class of unconventional electrocatalysts, two-dimensional (2D) metallene electrocatalysts with ultrathin sheet-like morphology have gained ever-growing attention and exhibited superior performance in electrocatalysis owing to their distinctive properties originating from structural anisotropy, rich surface chemistry, and efficient mass diffusion capability. Many significant advances in synthetic methods and electrocatalytic applications for 2D metallenes have been obtained in recent years. Therefore, an in-depth review summarizing the progress in developing 2D metallenes for electrochemical applications is highly needed. Unlike most reported reviews on the 2D metallenes, this review starts by introducing the preparation of 2D metallenes based on the classification of the metals (e.g., noble metals, and non-noble metals) instead of synthetic methods. Some typical strategies for preparing each kind of metal are enumerated in detail. Then, the utilization of 2D metallenes in electrocatalytic applications, especially in the electrocatalytic conversion reactions, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, fuel oxidation reaction, CO2 reduction reaction, and N2 reduction reaction, are comprehensively discussed. Finally, current challenges and opportunities for future research on metallenes in electrochemical energy conversion are proposed.

Designing reliable and accurate isotope-tracer experiments for CO2 photoreduction.

The photoreduction of carbon dioxide (CO2) into renewable synthetic fuels is an attractive approach for generating alternative energy feedstocks that may compete with and eventually displace fossil fuels. However, it is challenging to accurately trace the products of CO2 photoreduction on account of the poor conversion efficiency of these reactions and the imperceptible introduced carbon contamination. Isotope-tracing experiments have been used to solve this problem, but they frequently yield false-positive results because of improper experimental execution and, in some cases, insufficient rigor. Thus, it is imperative that accurate and effective strategies for evaluating various potential products of CO2 photoreduction are developed for the field. Herein, we experimentally demonstrate that the contemporary approach toward isotope-tracing experiments in CO2 photoreduction is not necessarily rigorous. Several examples of where pitfalls and misunderstandings arise, consequently making isotope product traceability difficult, are demonstrated. Further, we develop and describe standard guidelines for isotope-tracing experiments in CO2 photoreduction reactions and then verify the procedure using some reported photoreduction systems.

Electrochemical Lithium Extraction with Gas Flushing of Porous Electrodes.

Electrochemical extraction of lithium from seawater/brine is receiving more and more attention because of its environment-friendly and energy-saving features. In this work, an electrochemical lithium extraction system with gas flushing of porous electrodes is proposed. We verified that the operation of multiple gas washes can significantly reduce the consumption of ultrapure water during the solution exchange and save the time required for the continuous running of the system. The water consumption of multiple gas flush operations is only 1/60 of that of a normal single flush to obtain a purity close to 100% in the recovery solution. By comparing the ion concentration distribution on the electrode surface in flow-through and flow-by-flow modes, we demonstrate that the flow-through mode performs better. We also verified the lithium extraction performance of the whole system, achieving a purity close to 100% and average energy consumption of 0.732 kWh∙kg-1 in each cycle from the source solution of the simulated Atacama salt lake water. These results provide a feasible approach for the large-scale operation of electrochemical lithium extraction from seawater/brine.

Combined Photoredox Catalysis for Value-Added Conversion of Contaminants at Spatially Separated Dual Active Sites.

As 2 indispensable counterparts in one catalysis system, the independent reduction and oxidation reactions require synergetic regulation for cooperatively promoting redox efficiency. Despite the current success in promoting the catalytic efficiency of half reduction or oxidation reactions, the lack of redox integration leads to low energy efficiency and unsatisfied catalytic performance. Here, we exploit an emerging photoredox catalysis system by combining the reactions of nitrate reduction for ammonia synthesis and formaldehyde oxidation for formic acid production, in which superior photoredox efficiency is achieved on the spatially separated dual active sites of Ba single atoms and Ti3+. High catalytic redox rates are accomplished for respective ammonia synthesis (31.99 ± 0.79 mmol gcat -1 h-1) and formic acid production (54.11 ± 1.12 mmol gcat -1 h-1), reaching a photoredox apparent quantum efficiency of 10.3%. Then, the critical roles of the spatially separated dual active sites are revealed, where Ba single atoms as the oxidation site using h+ and Ti3+ as the reduction site using e- are identified, respectively. The efficient photoredox conversion of contaminants is accomplished with environmental importance and competitive economic value. This study also represents a new opportunity to upgrade the conventional half photocatalysis into the complete paradigm for sustainable solar energy utilization.

A possible systematic culinary approach for spent duck meat: sous-vide cuisine and its optimal cooking condition.

This study offered a possible systematic culinary approach to spent-laying ducks. Breast meat is suitable for processing due to its amount and completeness. Sous-vide cooking resulted in lower cooking loss than poaching, pan-frying (P < 0.05), and roasting. The sous-vide duck breast had higher gumminess, chewiness, and resilience than other culinary techniques (P < 0.05). Sous-vide cooking at 65°C had a lower cooking loss than 70°C (P < 0.05), and less than 1.5-h sous-vide could keep a lower cooking loss and WB shear value (P < 0.05) as the cooking period extended, the smaller (P < 0.05) quantity of myosin heavy chain and the destroyed sarcomere arrangement were observed. A condition at 65°C for 1.5 h could be the optimal sous-vide cuisine for spent-laying duck breast. These sous-vide products stored at 4°C were still safe for consumption due to no detectible microorganisms and unchangeable physicochemical properties within 7 d.

Photocatalytic CO2 reduction using La-Ni bimetallic sites within a covalent organic framework.

The precise construction of photocatalysts with diatomic sites that simultaneously foster light absorption and catalytic activity is a formidable challenge, as both processes follow distinct pathways. Herein, an electrostatically driven self-assembly approach is used, where phenanthroline is used to synthesize bifunctional LaNi sites within covalent organic framework. The La and Ni site acts as optically and catalytically active center for photocarriers generation and highly selective CO2-to-CO reduction, respectively. Theory calculations and in-situ characterization reveal the directional charge transfer between La-Ni double-atomic sites, leading to decreased reaction energy barriers of *COOH intermediate and enhanced CO2-to-CO conversion. As a result, without any additional photosensitizers, a 15.2 times enhancement of the CO2 reduction rate (605.8 µmol·g-1·h-1) over that of a benchmark covalent organic framework colloid (39.9 µmol·g-1·h-1) and improved CO selectivity (98.2%) are achieved. This work presents a potential strategy for integrating optically and catalytically active centers to enhance photocatalytic CO2 reduction.

Gradient Cationic Vacancies Enabling Inner-To-Outer Tandem Homojunctions: Strong Local Internal Electric Field and Reformed Basic Sites Boosting CO2 Photoreduction.

The slow charge dynamics and large activation energy of CO2 severely hinder the efficiency of CO2 photoreduction. Defect engineering is a well-established strategy, while the function of common zero-dimensional defects is always restricted to promoting surface adsorption. In this work, a gradient layer of tungsten vacancies with a thickness of 3-4 nm is created across Bi2 WO6 nanosheets. This gradient layer enables the formation of an inner-to-outer tandem homojunction with an internal electric field, which provides a strong driving force for the migration of photoelectrons from the bulk to the surface. Meanwhile, W vacancies change the coordination environment around O and W atoms, leading to an alteration in the basic sites and the mode of CO2 adsorption from weak/strong adsorption to moderate adsorption, which ultimately decreases the formation barrier of the key intermediate *COOH and facilitates the conversion thermodynamics for CO2 . Without any cocatalyst and sacrificial reagent, W-vacant Bi2 WO6 shows an outstanding photocatalytic CO2 reduction performance with a CO production rate of 30.62 µmol g-1  h-1 , being one of the best catalysts in similar reaction systems. This study reveals that gradient vacancies as a new type of defect will show huge potential in regulating charge dynamics and catalytic reaction thermodynamics.