Improving CO2 electroconversion by customizing the hydroxyl microenvironment around a semi-open Co-N2O2 configuration.

Constructing local microenvironments is one of the important strategies to improve the electrocatalytic performances, such as in electrochemical CO2 reduction (ECR). However, effectively customizing these microenvironments remains a significant challenge. Herein, utilizing carbon nanotube (CNT) heterostructured semi-open Co-N2O2 catalytic configurations (Co-salophen), we have demonstrated the role of the local microenvironment on promoting ECR through regulating the location of hydroxyl groups. Concretely, compared with the maximum Faradaic efficiency (FE) of 62% for carbon monoxide (CO) presented by Co-salophen/CNT without a hydroxyl microenvironment, the designed Co-salophen-OH3/CNT, featuring hydroxyl groups at the Co-N2O2 structural opening, shows remarkable CO2-to-CO electroreduction activity across a wide potential window, with the FE of CO up to 95%. In particular, through the deuterium kinetic isotope experiments and theoretical calculations, we decoded that the hydroxyl groups act as a proton relay station, promoting the efficient transfer of protons to the Co-N2O2 active sites. The finding demonstrates a promising molecular design strategy for enhancing electrocatalysis.

Bifunctional Oxygen-Defect Bismuth Catalyst toward Concerted Production of H2O2 with over 150% Cell Faradaic Efficiency in Continuously Flowing Paired-Electrosynthesis System.

The electrosynthesis of hydrogen peroxide (H2O2) from O2 or H2O via the two-electron (2e-) oxygen reduction (2e- ORR) or water oxidation (2e- WOR) reaction provides a green and sustainable alternative to the traditional anthraquinone process. Herein, a paired-electrosynthesis tactic is reported for concerted H2O2 production at a high rate by coupling the 2e- ORR and 2e- WOR, in which the bifunctional oxygen-vacancy-enriched Bi2O3 nanorods (Ov-Bi2O3-EO), obtained through electrochemically oxidative reconstruction of Bi-based metal-organic framework (Bi-MOF) nanorod precursor, are used as both efficient anodic and cathodic electrocatalysts, achieving concurrent H2O2 production at both electrodes with high Faradaic efficiencies. Specifically, the coupled 2e- ORR//2e- WOR electrolysis system based on such distinctive oxygen-defect Bi catalyst displays excellent performance for the paired-electrosynthesis of H2O2, delivering a remarkable cell Faradaic efficiency of 154.8% and an ultrahigh H2O2 production rate of 4.3 mmol h-1 cm-2. Experiments combined with theoretical analysis reveal the crucial role of oxygen vacancies in optimizing the adsorption of intermediates associated with the selective two-electron reaction pathways, thereby improving the activity and selectivity of the 2e- reaction processes at both electrodes. This work establishes a new paradigm for developing advanced electrocatalysts and designing novel paired-electrolysis systems for scalable and sustainable H2O2 electrosynthesis.

Screening Strategy Identifies an Overlooked Deep-Ultraviolet Transparent Nonlinear Optical Crystal.

In the deep-ultraviolet (DUV) region, nonlinear optical (NLO) crystals must meet stringent requirements, including a large optical band gap and sufficient second harmonic generation (SHG) response. Typically, these criteria are fulfilled by borates, carbonates and nitrates containing π-conjugated groups. In contrast, sulfates and phosphates, with polarizabilities significantly smaller than those of π-conjugated groups, struggle to achieve similar performance. Here, we present the discovery of Mg2PO4Cl, a magnesium-based phosphate, identified from over 10,000 phosphates based on a polar-axial-symmetry screening strategy, which exhibits the highest SHG response (5.2 × KH2PO4 (KDP)) with phase-matching ability among non-π-conjugated DUV transparent NLO crystals. This compound belongs to the Pna21 space group, with [PO4] units consistently aligned along the 21 screw axis and glide planes throughout its crystal structure. Theoretical calculations attribute its remarkable SHG effect to the orderly arrangement of heteroanionic [MgO5Cl] and [MgO4Cl2] polyhedra alongside isolated [PO4] tetrahedra, supported by Berry phase analysis. Furthermore, a crystallographic structure analysis of phosphates and sulfates with significant SHG effects validates the effectiveness of our screening strategy. These findings offer valuable insights into the origins of NLO effects in non-π-conjugated compounds from both a material design and structural chemistry perspective, inspiring future efforts to revitalize DUV phosphates.

Self-supported bimetallic array superstructures for high-performance coupling electrosynthesis of formate and adipate.

The coupling electrosynthesis involving CO2 upgrade conversion is of great significance for the sustainable development of the environment and energy but is challenging. Herein, we exquisitely constructed the self-supported bimetallic array superstructures from the Cu(OH)2 array architecture precursor, which can enable high-performance coupling electrosynthesis of formate and adipate at the anode and the cathode, respectively. Concretely, the faradaic efficiencies (FEs) of CO2-to-formate and cyclohexanone-to-adipate conversion simultaneously exceed 90% at both electrodes with excellent stabilities. Such high-performance coupling electrosynthesis is highly correlated with the porous nanosheet array superstructure of CuBi alloy as the cathode and the nanosheet-on-nanowire array superstructure of CuNi hydroxide as the anode. Moreover, compared to the conventional electrolysis process, the cell voltage is substantially reduced while maintaining the electrocatalytic performance for coupling electrosynthesis in the two-electrode electrolyzer with the maximal FEformate and FEadipate up to 94.2% and 93.1%, respectively. The experimental results further demonstrate that the bimetal composition modulates the local electronic structures, promoting the reactions toward the target products. Prospectively, our work proposes an instructive strategy for constructing adaptive self-supported superstructures to achieve efficient coupling electrosynthesis.

New evidence: Metformin unsuitable as routine adjuvant for breast cancer: a drug-target mendelian randomization analysis.

PURPOSE: The potential efficacy of metformin in breast cancer (BC) has been hotly discussed but never conclusive. This genetics-based study aimed to evaluate the relationships between metformin targets and BC risk. METHODS: Metformin targets from DrugBank and genome-wide association study (GWAS) data from IEU OpenGWAS and FinnGen were used to investigate the breast cancer (BC)-metformin causal link with various Mendelian Randomization (MR) methods (e.g., inverse-variance-weighting). The genetic association between type 2 diabetes (T2D) and the drug target of metformin was also analyzed as a positive control. Sensitivity and pleiotropic tests ensured reliability. RESULTS: The primary targets of metformin are PRKAB1, ETFDH and GPD1L. We found a causal association between PRKAB1 and T2D (odds ratio [OR] 0.959, P = 0.002), but no causal relationship was observed between metformin targets and overall BC risk (PRKAB1: OR 0.990, P = 0.530; ETFDH: OR 0.986, P = 0.592; GPD1L: OR 1.002, P = 0.806). A noteworthy causal relationship was observed between ETFDH and estrogen receptor (ER)-positive BC (OR 0.867, P = 0.018), and between GPD1L and human epidermal growth factor receptor 2 (HER2)-negative BC (OR 0.966, P = 0.040). Other group analyses did not yield positive results. CONCLUSION: The star target of metformin, PRKAB1, does not exhibit a substantial causal association with the risk of BC. Conversely, metformin, acting as an inhibitor of ETFDH and GPD1L, may potentially elevate the likelihood of developing ER-positive BC and HER2-negative BC. Consequently, it is not advisable to employ metformin as a standard supplementary therapy for BC patients without T2D.

Hierarchically Ordered Pore Engineering of Metal-Organic Framework-Based Materials for Electrocatalysis.

Ordered pore engineering that embeds uniform pores with periodic alignment in electrocatalysts opens up a new avenue for achieving further performance promotion. Hierarchically ordered porous metal-organic frameworks (HOP-MOFs) possessing multilevel pores with ordered distribution are the promising precursors for the exploration of ordered porous electrocatalysts, while the scalable acquisition of HOP-MOFs with editable components and adjustable pore size regimes is critical. This review presents recent progress on hierarchically ordered pore engineering of MOF-based materials for enhanced electrocatalysis. The synthetic strategies of HOP-MOFs with different pore size regimes, including the self-assembly guided by reticular chemistry, surfactant, nanoemulsion, and nanocasting, are first introduced. Then the applications of HOP-MOFs as the precursors for exploring hierarchically ordered porous electrocatalysts are summarized, selecting representatives to highlight the boosted performance. Especially, the intensification of molecule and ion transport integrated with optimized electron transfer and site exposure over the hierarchically ordered porous derivatives are emphasized to clarify the directional transfer and integration effect endowed by ordered pore engineering. Finally, the remaining scientific challenges and an outlook of this field are proposed. It is hoped that this review will guide the hierarchically ordered pore engineering of nanocatalysts for boosting the catalytic performance and promoting the practical applications.

Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate.

With the continuous development of laser technology and the increasing demand for lasers of different frequencies in the infrared (IR) spectrum, research on infrared nonlinear optical (NLO) crystals has garnered growing attention. Currently, the three main commercially available types of borate materials each have their drawbacks, which limit their applications in various areas. Rare-earth (RE)-based chalcogenide compounds, characterized by the unique f-electron configuration, strong positive charges, and high coordination numbers of RE cations, often exhibit distinctive optical responses. In the field of IR-NLO crystals, they have a research history spanning several decades, with increasing interest. However, there is currently no comprehensive review summarizing and analyzing these promising compounds. In this review, we categorize 85 representative examples out of more than 400 non-centrosymmetric (NCS) compounds into four classes based on the connection of different asymmetric building motifs: (1) RE-based chalcogenides containing tetrahedral motifs; (2) RE-based chalcogenides containing lone-pair-electron motifs; (3) RE-based chalcogenides containing [BS3] and [P2Q6] motifs; and (4) RE-based chalcohalides and oxychalcogenides. We provide detailed discussions on their synthesis methods, structures, optical properties, and structure-performance relationships. Finally, we present several favorable suggestions to further explore RE-based chalcogenide compounds. These suggestions aim to approach these compounds from a new perspective in the field of structural chemistry and potentially uncover hidden treasures within the extensive accumulation of previous research.

Ba10In2Mn11Si3O12S18: First Hexanary Oxychalcogenide Containing an Infrequent Three-Dimensional Noncentrosysmmetric Framework.

Noncentrosymmetric (NCS) oxychalcogenides have attracted great attention in recent years due to their immense potential as candidates for IR nonlinear-optical (NLO) applications. Despite notable advancements in this field, the discovery of oxychalcogenides with three-dimensional (3D) framework structures remains a formidable challenge. In this study, we report the discovery of the first hexanary oxychalcogenide, Ba10In2Mn11Si3O12S18, exhibiting second-order NLO activity, using a high-temperature solid-phase method. This compound showcases a novel structure type, featuring an uncommon NCS 3D [In2Mn11Si3O12S18]20- framework formed by vertex-sharing [(Mn/In)S6] octahedra, [(Mn/In)OS3] tetrahedra, and [SiO4] tetrahedra, with charge-balanced Ba2+ cations occupying the channels. Our study serves as a source of inspiration for researchers to further investigate the synthesis of novel NLO-active oxychalcogenides with 3D frameworks.

Breaking Through the Trade-Off Between Wide Band Gap and Large SHG Coefficient in Mercury-Based Chalcogenides for IR Nonlinear Optical Application.

It is substantially challenging for non-centrosymmetric (NCS) Hg-based chalcogenides for infrared nonlinear optical (IR-NLO) applications to realize wide band gap (Eg > 3.0 eV) and sufficient phase-matching (PM) second-harmonic-generation intensity (deff > 1.0 × benchmark AgGaS2 ) simultaneously due to the inherent incompatibility. To address this issue, this work presents a diagonal synergetic substitution strategy for creating two new NCS quaternary Hg-based chalcogenides, AEHgGeS4 (AE = Sr and Ba), based on the centrosymmetric (CS) AEIn2 S4 . The derived AEHgGeS4 displays excellent NLO properties such as a wide Eg (≈3.04-3.07 eV), large PM deff (≈2.2-3.0 × AgGaS2 ), ultra-high laser-induced damage threshold (≈14.8-15 × AgGaS2 ), and suitable Δn (≈0.19-0.24@2050 nm), making them highly promising candidates for IR-NLO applications. Importantly, such excellent second-order NLO properties are primarily attributed to the synergistic combination of tetrahedral [HgS4 ] and [GeS4 ] functional primitives, as supported by detailed theoretical calculations. This study reports the first two NCS Hg-based materials with well-balanced comprehensive properties (i.e., Eg > 3.0 eV and deff > 1.0 × benchmark AgGaS2 ) and puts forward a new design avenue for the construction of more efficient IR-NLO candidates.

Engineering Electronic and Morphological Structure of Metal-Organic-Framework-Derived Iron-Doped Ni2P/NC Hollow Polyhedrons for Enhanced Oxygen Evolution.

The rational design of an oxygen electrocatalyst with low cost and high activity is greatly desired for realization of the practical water-splitting industry. Herein, we put forward a rational method to construct nonprecious-metal catalysts with high activity by designing the microstructure and modulating the electronic state. Iron (Fe)-doped Ni2P hollow polyhedrons decorated with nitrogen-doped carbon (Fe-Ni2P/NC HPs) are prepared by a sequential metal-organic-framework-templated strategy. Benefiting from the strong electronic coupling, rapid charge-transfer capability, and abundant catalytic active sites, the obtained Fe-Ni2P/NC HPs exhibit an impressive electrocatalytic performance toward the oxygen evolution reaction (OER) with an ultralow overpotential of 228 mV at a current density of 10 mA cm-2 and a small Tafel slope of 33.4 mV dec-1, superior to the commercial RuO2 and most reported electrocatalysts. Notably, this catalyst also shows long durability with an almost negligible activity decay over 210 h for the OER. Combining density functional theory calculations with experiments demonstrates that the doped Fe and the incorporated carbon effectively modulate the electronic structure, enhance the conductivity, and greatly reduce the energy barrier of the rate-determining step in the process of OER. Thus, fast OER kinetics is realized. Moreover, this synthetic strategy can be extended to the synthesis of Fe-NiS2/NC HPs and Fe-NiSe2/NC HPs with excellent OER performance and long-term durability. This work furnishes an instructive idea in pursuit of nonprecious-metal materials with robust electrocatalytic activity and long durability.

Si Doping-Induced Electronic Structure Regulation of Single-Atom Fe Sites for Boosted CO2 Electroreduction at Low Overpotentials.

Transition metal-based single-atom catalysts (TM-SACs) are promising alternatives to Au- and Ag-based electrocatalysts for CO production through CO2 reduction reaction. However, developing TM-SACs with high activity and selectivity at low overpotentials is challenging. Herein, a novel Fe-based SAC with Si doping (Fe-N-C-Si) was prepared, which shows a record-high electrocatalytic performance toward the CO2-to-CO conversion with exceptional current density (>350.0 mA cm-2) and ~100% Faradaic efficiency (FE) at the overpotential of <400 mV, far superior to the reported Fe-based SACs. Further assembling Fe-N-C-Si as the cathode in a rechargeable Zn-CO2 battery delivers an outstanding performance with a maximal power density of 2.44 mW cm-2 at an output voltage of 0.30 V, as well as high cycling stability and FE (>90%) for CO production. Experimental combined with theoretical analysis unraveled that the nearby Si dopants in the form of Si-C/N bonds modulate the electronic structure of the atomic Fe sites in Fe-N-C-Si to markedly accelerate the key pathway involving *CO intermediate desorption, inhibiting the poisoning of the Fe sites under high CO coverage and thus boosting the CO2RR performance. This work provides an efficient strategy to tune the adsorption/desorption behaviors of intermediates on single-atom sites to improve their electrocatalytic performance.

Directional editing of self-supported nanoarray electrode for adaptive paired-electrolysis.

Anodic oxidation assisted hydrogen production under mild conditions powered by renewable electricity represents a sustainable approach to energy conversion systems. Here, we fabricated a versatile and universal self-supported nanoarray platform that can be intelligently edited to achieve adaptive electrocatalysis for alcohol oxidation reactions and hydrogen evolution reaction (HER). The obtained self-supported nanoarray electrocatalysts exhibit excellent catalytic activity due to the integration of multiple merits of rich nanointerface-reconstruction and self-supported hierarchical structures. Particularly, the membrane-free pair-electrolysis system coupling HER and ethylene glycol oxidation reaction (EGOR) required an applied voltage of only 1.25 V to drive the current density of 10 mA cm-2, which is about 510 mV lower than that of the overall water splitting, showing the capability to simultaneously produce H2 and formate with high Faradic efficiency and stability. This work demonstrates a catalytic self-supported nanoarray platform for energy-efficient production of high-purity H2 and value-added chemicals.

Rational Design of a Rare-Earth Oxychalcogenide Nd3 [Ga3 O3 S3 ][Ge2 O7 ] with Superior Infrared Nonlinear Optical Performance.

Inorganic chalcogenides have been studied as the most promising infrared (IR) nonlinear optical (NLO) candidates for the past decades. However, it is proven difficult to discover high-performance materials that combine the often-incompatible properties of large energy gap (Eg ) and strong second harmonic generation (SHG) response (deff ), especially for rare-earth chalcogenides. Herein, centrosymmetric Cs3 [Sb3 O6 ][Ge2 O7 ] is selected as a maternal structure and a new noncentrosymmetric rare-earth oxychalcogenide, namely, Nd3 [Ga3 O3 S3 ][Ge2 O7 ], is successfully designed and obtained by the module substitution strategy for the first time. Especially, Nd3 [Ga3 O3 S3 ][Ge2 O7 ] is the first case of breaking the trade-off relationship between wide Eg (>3.5 eV) and large deff (>0.5 × AgGaS2 ) in rare-earth chalcogenide system, and thus displays an outstanding IR-NLO comprehensive performance. Detailed structure analyses and theoretical studies reveal that the NLO effect originates mainly from the cooperation of heteroanionic [GaO2 S2 ] and [NdO2 S6 ] asymmetric building blocks. This work not only presents an excellent rare-earth IR-NLO candidate, but also plays a crucial role in the rational structure design of other NLO materials in which both large Eg and strong deff are pursued.

Introduction of Multicomponent Dyes into 2D MOFs: A Strategy to Fabricate White Light-Emitting MOF Composite Nanosheets.

Metal-organic frameworks (MOFs) have been extensively studied in host-guest chemistry by means of ultrahigh porosities, tunable channels, and component diversities. As the host matrix, MOFs exhibit immense potential in the preparation of single-phase white light-emitting (SPWLE) materials. Nonetheless, it is a great challenge that the size of the introduced guest molecules is limited by MOF pores, which affects the WLE optimization. In this work, two-dimensional (2D) MOFs are first utilized as the host matrices to simultaneously encapsulate red-green-blue fluorescent dyes for SPWLE. Various dyes@2D MOF composites with high-quality WLE performances and ultrathin nanosheet morphologies are directly assembled from 2D MOF precursors and dyes in high yields. Owing to the flexible interlamellar space of 2D MOFs, different types and sizes of guests can be easily introduced, which greatly expands the range of available MOF hosts and guests, making the WLE much more tunable. The strategy of employing 2D MOFs as the host matrices to introduce multicomponent dyes for SPWLE nanosheets resolves the restriction of MOF pores on the guest molecule size and opens a new avenue to rationally design and prepare SPWLE nanosheets that are highly solution-processable.

Ba5Ga2SiO4S6: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from Heteroanion Introduction.

Tailored structural regulation to obtain a new non-centrosymmetric (NCS) compound with excellent optical properties is highly desirable but remains a challenge for nonlinear optical (NLO) material design. In this work, centrosymmetric celsian-type BaGa2Si2O8 was selected as a template structure, and a novel NCS oxychalcogenide, namely, Ba5Ga2SiO4S6, was successfully designed via the introduction of heteroanions under high-temperature solid-state conditions. Ba5Ga2SiO4S6 adopts the monoclinic space group of Cc (no. 9) and is formed by charges balancing Ba2+ cations and discrete [Ga2SiO4S6] clusters made of corner-sharing [SiO4] and [GaOS3] tetrahedra. Notably, Ba5Ga2SiO4S6 exhibits the critical requirements as a potential UV NLO candidate, including a phase-matching second-harmonic generation intensity (∼1.0 × KDP), a beneficial laser-induced damage threshold (1.2 × KDP), a large birefringence (Δn = 0.10@546 nm), and a short UV absorption cutoff edge (ca. 0.26 µm). Furthermore, the theoretical calculation is implemented to provide a deeper analysis of the structure-activity relationship. The investigated example of structural regulation originated from heteroanion introduction in this study may offer a feasible strategy for high-performance NLO candidate design.

Rational design via dual-site aliovalent substitution leads to an outstanding IR nonlinear optical material with well-balanced comprehensive properties.

The acquisition of a non-centrosymmetric (NCS) structure and achieving a nice trade-off between a large energy gap (E g > 3.5 eV) and a strong second-harmonic generation (SHG) response (d eff > 1.0 × benchmark AgGaS2) are two formidable challenges in the design and development of infrared nonlinear optical (IR-NLO) candidates. In this work, a new quaternary NCS sulfide, SrCdSiS4, has been rationally designed using the centrosymmetric SrGa2S4 as the template via a dual-site aliovalent substitution strategy. SrCdSiS4 crystallizes in the orthorhombic space group Ama2 (no. 40) and features a unique two-dimensional [CdSiS4]2- layer constructed from corner- and edge-sharing [CdS4] and [SiS4] basic building units (BBUs). Remarkably, SrCdSiS4 displays superior IR-NLO comprehensive performances, and this is the first report on an alkaline-earth metal-based IR-NLO material that breaks through the incompatibility between a large E g (>3.5 eV) and a strong phase-matching d eff (>1.0 × AgGaS2). In-depth mechanism explorations strongly demonstrate that the synergistic effect of distorted tetrahedral [CdS4] and [SiS4] BBUs is the main origin of the strong SHG effect and large birefringence. This work not only provides a high-performance IR-NLO candidate, but also offers a feasible chemical design strategy for constructing NCS structures.

Oxychalcogenides as Promising Ultraviolet Nonlinear Optical Candidates: Experimental and Theoretical Studies of AEGeOS2 (AE = Sr and Ba).

Oxychalcogenides have gained widespread attention as promising infrared nonlinear optical (IR-NLO) candidates. However, high-performance oxychalcogenides have rarely been reported in the ultraviolet (UV) region owing to the low energy gaps (Eg < 4.0 eV). Herein, two non-centrosymmetric (NCS) oxychalcogenides with one-dimensional (1D) chain structures and wide Eg (>4.3 eV), namely, AEGeOS2 (AE = Sr and Ba), have been discovered by combined experiments and theory calculations as a new source of UV-NLO materials. Significantly, they exhibit excellent comprehensive performance comparable to the commercial UV-NLO material KH2PO4 (KDP), including large phase-matching ranges (>380 nm), sufficient second harmonic generation intensities (0.7-1.1 × KDP), high laser-induced damage thresholds (1.2 × KDP), wide transparent regions (0.26-12.2 µm), and good thermal stability (up to 1100 K). Moreover, systematic structure-activity relationship analysis illustrates that the 1D homochiral helical [GeOS2]2- chains composed of heteroanionic [GeS2O2] units make major contribution to the desirable UV-NLO performance. This work makes the two compounds shine out as new energy in the UV-NLO field and offers a new perspective for the exploration of structure-driven functional oxychalcogenides.

Enzyme-Inspired Microenvironment Engineering of a Single-Molecular Heterojunction for Promoting Concerted Electrochemical CO2 Reduction.

Challenges remain in the development of novel multifunctional electrocatalysts and their industrial operation on low-electricity pair-electrocatalysis platforms for the carbon cycle. Herein, an enzyme-inspired single-molecular heterojunction electrocatalyst ((NHx )16 -NiPc/CNTs) with specific atomic nickel centers and amino-rich local microenvironments for industrial-level electrochemical CO2 reduction reaction (eCO2 RR) and further energy-saving integrated CO2 electrolysis is designed and developed. (NHx )16 -NiPc/CNTs exhibit unprecedented catalytic performance with industry-compatible current densities, ≈100% Faradaic efficiency and remarkable stability for CO2 -to-CO conversion, outperforming most reported catalysts. In addition to the enhanced CO2 capture by chemisorption, the sturdy deuterium kinetic isotope effect and proton inventory studies sufficiently reveal that such distinctive local microenvironments provide an effective proton ferry effect for improving local alkalinity and proton transfer and creating local interactions to stabilize the intermediate, ultimately enabling the high-efficiency operation of eCO2 RR. Further, by using (NHx )16 -NiPc/CNTs as a bifunctional electrocatalyst in a flow cell, a low-electricity overall CO2 electrolysis system coupling cathodic eCO2 RR with anodic oxidation reaction is developed to achieve concurrent feed gas production and sulfur recovery, simultaneously decreasing the energy input. This work paves the new way in exploring molecular electrocatalysts and electrolysis systems with techno-economic feasibility.

Quaternary Noncentrosymmetric Rare-Earth Sulfides Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb): A Joint Experimental and Theoretical Investigation.

Multinary rare-earth chalcogenides with d-block transition metals have attracted considerable attention owing to their intriguing structural architectures and promising practical applications. In this work, three quaternary rare-earth sulfides, Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb), have been obtained by the high-temperature solid-state method. These compounds are isostructural and belong to the noncentrosymmetric orthorhombic space group Cmc21 (No. 36). The basic structural unit contains unique two-dimensional anionic [RE2Cd3S10]8- layers, which are separated by Ba2+ cations. Remarkably, Ba4Sm2Cd3S10 exhibits a high second-harmonic-generation intensity (1.8 times that of AgGaS2) and a significantly higher laser-induced damage threshold (14.3 times that of AgGaS2), which is the first case possessing an infrared (IR) nonlinear optical (NLO) property in the quaternary AE/RE/TM/Q (AE = alkaline-earth metals; RE = rare-earth metals; TM = d-block transition metals; and Q = chalcogen) systems. Moreover, theoretical investigations of the structure-property relationship indicate that the combined action of various types of NLO-active units makes the main contribution to the SHG activity. This discovery may shed light on broadening the frontiers of IR-NLO materials.

Integrated 3D Open Network of Interconnected Bismuthene Arrays for Energy-Efficient and Electrosynthesis-Assisted Electrocatalytic CO2 Reduction.

Electrocatalytic CO2 reduction reaction (CO2 RR) toward formate production can be operated under mild conditions with high energy conversion efficiency while migrating the greenhouse effect. Herein, an integrated 3D open network of interconnected bismuthene arrays (3D Bi-ene-A/CM) is fabricated via in situ electrochemically topotactic transformation from BiOCOOH nanosheet arrays supported on the copper mesh. The resulted 3D Bi-ene-A/CM consists of 2D atomically thin metallic bismuthene (Bi-ene) in the form of an integrated array superstructure with a 3D interconnected and open network, which harvests the multiple structural advantages of both metallenes and self-supported electrodes for electrocatalysis. Such distinctive superstructure affords the maximized quantity and availability of the active sites with high intrinsic activity and superior charge and mass transfer capability, endowing the catalyst with good CO2 RR performance for stable formate production with high Faradaic efficiency (≈90%) and current density (>300 mA cm-2 ). Theoretical calculation verifies the superior intermediate stabilization of the dominant Bi plane during CO2 RR. Moreover, by further coupling anodic methanol oxidation reaction, an exotic electrolytic system enables highly energy-efficient and value-added pair-electrosynthesis for concurrent formate production at both electrodes, achieving substantially improved electrochemical and economic efficiency and revealing the feasibility for practical implementation.