Interlayer Affected Diamond Electrochemistry.

Diamond electrochemistry is primarily influenced by quantities of sp3-carbon, surface terminations, and crystalline structure. In this work, a new dimension is introduced by investigating the effect of using substrate-interlayers for diamond growth. Boron and nitrogen co-doped nanocrystalline diamond (BNDD) films are grown on Si substrate without and with Ti and Ta as interlayers, named BNDD/Si, BNDD/Ti/Si, and BNDD/Ta/Ti/Si, respectively. After detailed characterization using microscopies, spectroscopies, electrochemical techniques, and density functional theory simulations, the relationship of composition, interfacial structure, charge transport, and electrochemical properties of the interface between diamond and metal is investigated. The BNDD/Ta/Ti/Si electrodes exhibit faster electron transfer processes than the other two diamond electrodes. The interlayer thus determines the intrinsic activity and reaction kinetics. The reduction in their barrier widths can be attributed to the formation of TaC, which facilitates carrier tunneling, and simultaneously increases the concentration of electrically active defects. As a case study, the BNDD/Ta/Ti/Si electrode is further employed to assemble a redox-electrolyte-based supercapacitor device with enhanced performance. In summary, the study not only sheds light on the intricate relationship between interlayer composition, charge transfer, and electrochemical performance but also demonstrates the potential of tailored interlayer design to unlock new capabilities in diamond-based electrochemical devices.

Engineering Triple-Phase Interfaces around the Anode toward Practical Alkali Metal-Air Batteries.

Alkali metal-air batteries (AMABs) promise ultrahigh gravimetric energy densities, while the inherent poor cycle stability hinders their practical application. To address this challenge, most previous efforts are devoted to advancing the air cathodes with high electrocatalytic activity. Recent studies have underlined the solid-liquid-gas triple-phase interface around the anode can play far more significant roles than previously acknowledged by the scientific community. Besides the bottlenecks of uncontrollable dendrite growth and gas evolution in conventional alkali metal batteries, the corrosive gases, intermediate oxygen species, and redox mediators in AMABs cause more severe anode corrosion and structural collapse, posing greater challenges to the stabilization of the anode triple-phase interface. This work aims to provide a timely perspective on the anode interface engineering for durable AMABs. Taking the Li-air battery as a typical example, this critical review shows the latest developed anode stabilization strategies, including formulating electrolytes to build protective interphases, fabricating advanced anodes to improve their anti-corrosion capability, and designing functional separator to shield the corrosive species. Finally, the remaining scientific and technical issues from the prospects of anode interface engineering are highlighted, particularly materials system engineering, for the practical use of AMABs.

On-Chip Micro Temperature Controllers Based on Freestanding Thermoelectric Nano Films for Low-Power Electronics.

Multidimensional integration and multifunctional component assembly have been greatly explored in recent years to extend Moore's Law of modern microelectronics. However, this inevitably exacerbates the inhomogeneity of temperature distribution in microsystems, making precise temperature control for electronic components extremely challenging. Herein, we report an on-chip micro temperature controller including a pair of thermoelectric legs with a total area of 50 × 50 µm2, which are fabricated from dense and flat freestanding Bi2Te3-based thermoelectric nano films deposited on a newly developed nano graphene oxide membrane substrate. Its tunable equivalent thermal resistance is controlled by electrical currents to achieve energy-efficient temperature control for low-power electronics. A large cooling temperature difference of 44.5 K at 380 K is achieved with a power consumption of only 445 µW, resulting in an ultrahigh temperature control capability over 100 K mW-1. Moreover, an ultra-fast cooling rate exceeding 2000 K s-1 and excellent reliability of up to 1 million cycles are observed. Our proposed on-chip temperature controller is expected to enable further miniaturization and multifunctional integration on a single chip for microelectronics.

Design and synthesis of hierarchical MnO-Fe3O4@C/expanded graphite composite for sensitive electrochemical detection of bisphenol A.

Hierarchically nanostructured binary transition metal oxide-based materials with high conductivity and catalytic activity are quite attractive for the electrochemical quantitative detection of environmental pollutants due to their natural abundance, variable oxidation state, and excellent synergies between metal sites. Herein, a new hierarchical MnO-Fe3O4@C/expanded graphite (EG) composite is designed and synthesized through a simple and in situ annealing method with the utilization of bimetallic organic framework (FeMn-MOF)/EG precursor. The synthesized MnO-Fe3O4@C/EG composite possesses a unique hierarchical nanoarchitecture that small-sized bimetallic oxide nanoparticles of 10-40 nm completely encapsulated by amorphous carbon layers of 2-4 nm are uniformly distributed on the EG platform. This distinctive structure combines the advantages of high conductivity, excellent catalytic activity, and strong stability. Resultantly, when it is applied to monitor environmental endocrine disruptors, the sensor exhibits a significant catalytic effect on the electrochemical oxidation of bisphenol A (BPA), inducing an amplified response current. In addition, the sensor shows a wide linear range of 1-50 µM and 50-400 µM for the BPA monitor, giving a sensitivity of 5208.8 and 1641.9 µA mM-1 cm-2, respectively. This study offers a new approach to design hierarchical binary metal oxide-based sensing materials as well as to explore their electrochemical properties and applications for the determination of emerging contaminants.

Aptamer-functionalized field-effect transistor biosensors for disease diagnosis and environmental monitoring.

Nano-biosensors that are composed of recognition molecules and nanomaterials have been extensively utilized in disease diagnosis, health management, and environmental monitoring. As a type of nano-biosensors, molecular specificity field-effect transistor (FET) biosensors with signal amplification capability exhibit prominent advantages including fast response speed, ease of miniaturization, and integration, promising their high sensitivity for molecules detection and identification. With intrinsic characteristics of high stability and structural tunability, aptamer has become one of the most commonly applied biological recognition units in the FET sensing fields. This review summarizes the recent progress of FET biosensors based on aptamer functionalized nanomaterials in medical diagnosis and environmental monitoring. The structure, sensing principles, preparation methods, and functionalization strategies of aptamer modified FET biosensors were comprehensively summarized. The relationship between structure and sensing performance of FET biosensors was reviewed. Furthermore, the challenges and future perspectives of FET biosensors were also discussed, so as to provide support for the future development of efficient healthcare management and environmental monitoring devices.

High-Performance Supercapacitors Using Hierarchical And Sulfur-Doped Trimetallic NiCo/NiMn Layered Double Hydroxides.

A supercapacitor features high power density and long cycling life. However, its energy density is low. To ensemble a supercapacitor with high power- and energy-densities, the applied capacitor electrodes play the key roles. Herein, a high-performance capacitive electrode is designed and grown on a flexible carbon cloth (CC) substrate via a hydrothermal reaction and a subsequent ion exchange sulfuration process. It has a 3D heterostructure, consisting of sulfur-doped NiMn-layered double hydroxide (LDH) nanosheets (NMLS) and sulfur-doped NiCo-LDH nanowires (NCLS). The electrode with sheet-shaped NMLS and wire-shaped NCLS on their top (NMLS@NCLS/CC) increases the available surface area, providing more pseudocapacitive sites. It exhibits a gravimetric capacity of 555.2 C g-1 at a current density of 1 A g-1 , the retention rate of 75.1% when the current density reaches up to 20 A g-1 , as well as superior cyclic stability. The assembled asymmetric supercapacitor that is composed of a NMLS@NCLS/CC positive electrode and a sulfurized activated carbon negative electrode presents a maximum energy density of 24.2 Wh kg-1 and a maximum power density of 16000 W kg-1 . In this study, a facile strategy for designing hierarchical LDH materials is demonstrated as well as their applications in advanced energy storage systems.

Regulating d-Band Center of Ti2 C MXene Via Nb Alloying for Stable and High-Efficient Supercapacitive Performances.

Ti2 C MXene with the lowest formula weight is expected to gain superior advantages in gravimetric capacitances over other heavier MXenes. Nevertheless, its poor chemical and electrochemical stability is the most fatal drawback and seriously hinders its practical applications. Herein, an alloy engineering strategy at the transition metal-sites of Ti2 C MXene is proposed. Theoretical calculations reveal that the electronic redistribution of the solid-solution TiNbC MXene improves the electronic conductivity, induces the upward d-band center, tailors the surface functional groups, and increases the electron loss impedance, resulting in its excellent capacitive performance and high chemical stability. The as-prepared flexible TiNbC film delivers specific capacitance up to 381 F g-1 at a scan rate of 2 mV s-1 and excellent electrochemical stability without capacitance loss after 10000 charge/discharging cycles. This work provides a universal approach to develop high-performance and chemically stable MXene electrodes.

Photocatalytic and Electrocatalytic Generation of Hydrogen Peroxide: Principles, Catalyst Design and Performance.

Hydrogen peroxide (H2O2) is a high-demand organic chemical reagent and has been widely used in various modern industrial applications. Currently, the prominent method for the preparation of H2O2 is the anthraquinone oxidation. Unfortunately, it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards. In this context, numerous approaches have been developed to synthesize H2O2. Among them, photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H2O2. These alternatives are sustainable in that only water or O2 is required. Namely, water oxidation (WOR) or oxygen reduction (ORR) reactions can be further coupled with clean and sustainable energy. For photo/electro-catalytic reactions for H2O2 generation, the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance. This article overviews the basic principles of WOR and ORR, followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H2O2 generation. The related mechanisms for these approaches are highlighted from theoretical and experimental aspects. Scientific challenges and opportunities of engineering photo/electro-catalysts for H2O2 generation are also outlined and discussed.

Size-Dependent Electrochemistry of Oxygenated Ti3 C2 Tx MXenes.

2D MXenes are widely proved to be potential electrode materials, although the size effect on their electrochemistry is not fully understood. In this work, Ti3 C2 Tx nanoflakes are prepared through acidic etching of Ti3 AlC2 powders, followed by the intercalation treatment with tetrapropylammonium hydroxide. Such a method produces large-scale delaminated and oxygenated nanoflakes. With aid of centrifugation, the nanoflakes with varied lateral sizes and thicknesses are collected, where electrochemical response of charged redox probes and polar phenol molecules is varied. Density functional theory and energy dispersive spectroscopy confirm such electrochemical response is dependent on the size and thickness of used nanoflakes, more exactly the oxygen content on their surface. Taking the nanoflakes obtained using a centrifugal speed of 5000 rpm (MX-TPA0.2 ) as an example, they feature good dispersibility, a high oxygen content, a small size, and a thin thickness. On these nanoflakes electrochemical response of polar p-substituted phenols is pronounced, stemming from a strong electron-withdrawing interaction of their oxygenated termination with the Ar-OH. A sensitive electrochemical sensor is further constructed for the detection of p-nitrophenol. This work thus provides an approach to synthesize MXenes with different sizes and thicknesses as well as further to reveal size-dependent electrochemistry of MXenes.

Carbon nanopores for DNA sequencing: a review on nanopore materials.

In the past few decades, nanometer-scale pores have been employed as a powerful tool for sensing biological molecules. In pursuit of this technology, a variety of nanotechnology-based approaches have been explored and established, especially nanopore sequencing. In comparison to the existing pores in other materials such as Si3N4, carbon nanopores have the ability to rapidly sense various biological molecules at single-molecule resolution and with reduced cost. Different from most reviews about nanopore sequencing, herein, we focus on the nanopore materials employed for sequencing applications. Initially, we provide an overview on the general issues associated with nanopore sequencing, concentrating on the recent progress and achievements in nanopore sequencing, especially using various carbon nanomaterials such as graphene and carbon nanotubes. Finally, the future research directions using carbon nanomaterials for nanopore sequencing are discussed and outlined.

Interfacial superassembly of flower-like NiMn-LDH@poly-l-lysine composites for selective electrochemical sensing of tryptophan.

Development of sensitive, selective, and facile electrochemical analytical approaches to monitor tryptophan in different samples is of high significance. For such approaches, efficient electrodes play the key role. Herein, a NiMn-layered double hydroxide (LDH)@poly-l-lysine (PLL) composite has been prepared through in-situ electro-polymerization and further utilized to monitor tryptophan in medicament and biological systems. The as-synthesized NiMn-LDH@PLL composite is highly stable and features a flower-like morphology. It is found that the electron transfer rate of NiMn-LDH@PLL is greatly improved due to the introduction of PLL. The existing Lewis acid-base interaction between LDH and PLL contributes to the increase of unsaturated metal sites and endows this heterojunction composite with high electrocatalytic activity. Especially, the NiMn-LDH (2:1)@PLL composite displays much improved electrochemical response toward tryptophan sensing. This is due to reasonable balance between the outstanding electrocatalytic ability of nickel and the conductivity improvement caused by manganese species. On the other hand, the coordination promotion between NiMn-LDH and PLL is also conducive to improve the sensitivity of electrochemical response. The fabricated sensor exhibits wide linear response in the concentration ranges of 0.1-40 µM and 40-130 µM for tryptophan detection, along with a low detection limit of 52.7 nM. It further displays a high anti-interference ability for tryptophan monitoring even in the presence of other coexistent amino acids and small-sized biological molecules. This study provides a new way to employ LDHs as brilliant sensing platform to ensemble electrochemical sensors for the monitoring of biomolecules.

Rational Design of Diamond Electrodes.

Diamond electrodes stepped onto the stage in the early 1990s for electroanalytical applications. They possess the features of long-term chemical inertness, wide potential windows, low and stable background currents, high microstructural stability at different potentials and in different media, varied activity toward different electroactive species, reliable electrochemical response of redox systems without conventional pretreatment, high resistance to surface fouling in most cases, and possibility of forming composites with different components such as other carbon materials, carbides, and oxidizes. Most diamond electrodes are prepared in microcrystalline or nanocrystalline form using chemical vapor deposition techniques. Starting from diamond films and diamond composites, numerous nanostructured diamond electrodes have also been produced. The features of diamond electrodes are therefore heavily dependent on the growth conditions and post-treatment procures that are applied on diamond electrodes such as introduced dopant(s), surface termination(s), surface functional group(s), added components, and final structure(s). Numerous applications of diamond electrodes have been explored in the fields of electrochemical sensing, electrosynthesis, electrocatalysis, electrochemical energy storage and conversion, devices, and environmental degradation.This Account summarizes our strategies to design different diamond electrodes, including diamond films, diamond composites, as well as their nanostructures. With respect to diamond films, the modulation of their dopant(s) and surface termination(s) as well as the attachment of functional modifier(s) onto their surface are discussed. Electrochemical hydrogenation and oxygenation of diamond electrodes are detailed at an atomic scale. As the examples of designing diamond electrodes at a molecular scale, photochemical and electrochemical attachment of modifier(s) onto diamond electrodes are shown. Moreover, electrochemical grafting of diazonium salts is proposed as a new technique to identify hydrogenated, hydroxylated, and oxygenated terminations of diamond electrodes. The introduction of additional component(s) into a diamond film to form diamond composites is then overviewed, where a hydrogen-induced selective growth model is proposed to elucidate the preparation of diamond/ß-SiC composites. Subsequently, the production of various diamond nanostructures from diamond films and composites by means of top-down, bottom-up, and template-free approaches is shown. Electrochemical application examples of diamond electrodes are overviewed, covering direct electrochemistry of natural Cytochrome c on a hydroxylated diamond surface, sensitive electrochemical DNA biosensing on tip-functionalized diamond nanowires, and construction of high-performance supercapacitors using diamond electrodes and redox electrolytes. Our diamond supercapacitors, also named battery-like diamond supercapacitors or diamond supercabatteries, are highlighted since they combine the features of supercapacitors and batteries. Future perspectives of diamond electrodes are outlined, ranging from their rational design and synthesis to their electrochemical applications in different fields.

Manipulating Deposition Behavior by Polymer Hydrogel Electrolyte Enables Dendrite-Free Zinc Anode for Zinc-Ion Hybrid Capacitors.

Rechargeable aqueous zinc-ion hybrid capacitors (ZHCs) have aroused unprecedented attention because of their high safety, cost effectiveness, and environmental compatibility. However, the intractable issues of dendrite growth and side reactions at the electrode-electrolyte interface deteriorate durability and reversibility of Zn anodes, deeply encumbering the large-scale application of ZHCs. Concerning these obstacles, a negatively charged carboxylated chitosan-intensified hydrogel electrolyte (CGPPHE) with cross-linked networks is reported to stabilize Zn anodes. Beyond possessing good mechanical characteristics, the CGPPHE with polar groups can reduce the desolvation energy barrier of hydrated Zn2+ , constrain the 2D Zn2+ diffusion, and uniformize electric field and Zn2+ flux distributions, assuring dendrite-free Zn deposition with high plating-stripping efficiency. Concurrently, the hydrophilic CGPPHE alleviates harmful hydrogen evolution and corrosion by abating water activity. Accordingly, Zn|CGPPHE|Zn and Zn|CGPPHE|Cu cells exhibit an extended life exceeding 350 h (1600 mAh cm-2 cumulative capacity under 20 mA cm-2 ) and a high average coulombic efficiency of 98.2%, respectively. The resultant flexible ZHCs with CGPPHE and template-regulated carbon cathode present perfect properties in capacity retention (97.7% over 10 000 cycles), energy density (91.8 Wh kg-1 ), and good mechanical adaptability. This study provides insight into developing novel hydrogel electrolytes toward highly rechargeable and stable ZHCs.

Coupling W18 O49 /Ti3 C2 Tx MXene Pseudocapacitive Electrodes with Redox Electrolytes to Construct High-Performance Asymmetric Supercapacitors.

A pseudocapacitive electrode with a large surface area is critical for the construction of a high-performance supercapacitor. A 3D and interconnected network composed of W18 O49 nanoflowers and Ti3 C2 Tx MXene nanosheets is thus synthesized using an electrostatic attraction strategy. This composite effectively prevents the restacking of Ti3 C2 Tx MXene nanosheets and meanwhile sufficiently exposes electrochemically active sites of W18 O49 nanoflowers. Namely, this self-assembled composite owns abundant oxygen vacancies from W18 O49 nanoflowers and enough active sites from Ti3 C2 Tx MXene nanosheets. As a pseudocapacitive electrode, it shows a big specific capacitance, superior rate capability and good cycle stability. A quasi-solid-state asymmetric supercapacitor (ASC) is then fabricated using this pseudocapacitive anode and the cathode of activated carbon coupled with a redox electrolyte of FeBr3 . This ASC displays a cell voltage of 1.8 V, a capacitance of 101 F g-1 at a current density of 1 A g-1 , a maximum energy density of 45.4 Wh kg-1 at a power density of 900 W kg-1 , and a maximum power density of 18 000 W kg-1 at an energy density of 10.8 Wh kg-1 . The proposed strategies are promising to synthesize different pseudocapacitive electrodes as well as to fabricate high-performance supercapacitor devices.

Advances in Biomimetic Photoelectrocatalytic Reduction of Carbon Dioxide.

Emerging photoelectrocatalysis (PEC) systems synergize the advantages of electrocatalysis (EC) and photocatalysis (PC) and are considered a green and efficient approach to CO2 conversion. However, improving the selectivity and conversion rate remains a major challenge. Strategies mimicking natural photosynthesis provide a prospective way to convert CO2 with high efficiency. Herein, several typical strategies are described for constructing biomimetic photoelectric functional interfaces; such interfaces include metal cocatalysts/semiconductors, small molecules/semiconductors, molecular catalysts/semiconductors, MOFs/semiconductors, and microorganisms/semiconductors. The biomimetic PEC interface must have enhanced CO2 adsorption capacity, preferentially activate CO2 , and have an efficient conversion ability; with these properties, it can activate CO bonds effectively and promote electron transfer and CC coupling to convert CO2 to single-carbon or multicarbon products. Interfacial electron transfer and proton coupling on the biomimetic PEC interface are also discussed to clarify the mechanism of CO2 reduction. Finally, the existing challenges and perspectives for biomimetic photoelectrocatalytic CO2 reduction are presented.

Graphdiyne Electrochemistry: Progress and Perspectives.

Graphdiyne, a carbon allotrope, was synthesized in 2010 for the first time. It consists of two acetylene bonds between adjacent benzene rings. Graphdiyne and its composites thus exhibit ultrahigh intrinsic electrochemical activities. As "star" electrode materials, they have been utilized for various electrochemical applications. With the aim of giving a full screen of graphdiyne electrochemistry, this review starts from the history of graphdiyne materials, followed by their structural and electrochemical features. Recent progress and achievements in the synthesis of graphdiyne materials and their composites are overviewed. Subsequently, various electrochemical applications of graphdiyne materials and their composites are summarized, covering those in the fields of electrochemical energy conversion, electrochemical energy storage, and electrochemical sensing. The perspectives of graphdiyne electrochemistry are also discussed and outlined.

Electrochemical Capacitors with Confined Redox Electrolytes and Porous Electrodes.

Electrochemical capacitors (ECs), including electrical-double-layer capacitors and pseudocapacitors, feature high power densities but low energy densities. To improve the energy densities of ECs, redox electrolyte-enhanced ECs (R-ECs) or supercapbatteries are designed through employing confined soluble redox electrolytes and porous electrodes. In R-ECs the energy storage is based on diffusion-controlled faradaic processes of confined redox electrolytes at the surface of a porous electrode, which thus take the merits of high power densities of ECs and high energy densities of batteries. In the past few years, there has been great progress in the development of this energy storage technology, particularly in the design and synthesis of novel redox electrolytes and porous electrodes, as well as the configurations of new devices. Herein, a full-screen picture of the fundamentals and the state-of-art progress of R-ECs are given together with a discussion and outlines about the challenges and future perspectives of R-ECs. The strategies to improve the performance of R-ECs are highlighted from the aspects of their capacitances and capacitance retention, power densities, and energy densities. The insight into the philosophies behind these strategies will be favorable to promote the R-EC technology toward practical applications of supercapacitors in different fields.

Freeze-Tolerant Hydrogel Electrolyte with High Strength for Stable Operation of Flexible Zinc-Ion Hybrid Supercapacitors.

Constructing ionic conductive hydrogels with diversified properties is crucial for portable zinc-ion hybrid supercapacitors (ZHSCs). Herein, a freeze-tolerant hydrogel electrolyte (AF PVA-CMC/Zn(CF3 SO3 )2 ) is developed by forming a semi-interpenetrating anti-freezing polyvinyl alcohol-carboxymethyl cellulose (AF PVA-CMC) network filled with the ethylene glycol (EG)-containing Zn(CF3 SO3 )2 aqueous solution. The semi-interpenetrating AF PVA-CMC/Zn(CF3 SO3 )2 possesses enhanced mechanical properties, realizes the uniform zinc deposition, and impedes the dendrite growth. Notably, the interaction between PVA and EG suppresses the ice crystal formation and prevents freezing at -20 °C. Due to these advantages, the designed hydrogel owns high ionic conductivity of 1.73/0.75 S m-1 at 20/-20 °C with excellent tensile/compression strength at 20 °C. Impressively, the flexible AF quasi-solid-state ZHSC employing the hydrogel electrolyte achieves a superior energy density at 20/-20 °C (87.9/60.7 Wh kg-1 ). It maintains nearly 84.8% of the initial capacity after 10 000 cycles and a low self-discharge rate (1.77 mV h-1 ) at 20 °C, together with great tolerance to corrosion. Moreover, this device demonstrates a stable electrochemical performance at -20 °C under deformation. The obtained results provide valuable insights for constructing durable hydrogel electrolytes in cold environments.

Metal Centers and Organic Ligands Determine Electrochemistry of Metal-Organic Frameworks.

The properties and applications of metal-organic frameworks (MOFs) can be tuned by their metal centers and organic ligands. To reveal experimentally and theoretically the influence of metal centers and ligands on electrochemical performance of MOFs, three MOFs with copper or zinc centers and organic ligands of 2-methylimidazole (2MI) or 1,3,5-benzenetricarboxylic acid (H3 BTC) are synthesized and characterized in this study. 2D and porous Cu-2MI exhibits a larger active area, faster electron transfer capability, and stronger adsorption capacity than bulk Cu-BTC and dodecahedron Zn-2MI. Density functional theory calculations of adsorption ability of three MOFs toward xanthine (XA), hypoxanthine (HXA), and malachite green (MG) prove that 2D Cu-2MI has the strongest adsorption energies to three targets. Rotating disk electrode measurements reveal that 2D Cu-2MI features the biggest intrinsic heterogeneous rate constant toward three analytes. On 2D Cu-2MI sensitive and selective monitoring of XA, HXA, and MG is then achieved using differential pulse voltammetry. Their monitoring in real samples on 2D Cu-2MI is accurate and comparable with that using high-performance liquid chromatography. In summary, regulation of electrochemical sensing features of MOFs is realized through defining selected metal centers and organic ligands.