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Niobium oxide exists in several crystal phases and valence states, yielding a variety of properties. Phase transitions between polymorphs significantly alter the properties of functional niobium oxide nanostructures, which are applied in many different renewable energy applications. This study uses environmental transmission electron microscopy to investigate the oxidation of NbO nanowires to T-Nb2O5. Small oxygen partial pressures (

Extending the portfolio of novel stimuli-responsive, high-refractive-index (RI) materials besides titania is key to improve the optical quality and sensing performance of existing photonic devices. Herein, lithium tin sulfide (LTS) nanosheets are introduced as a novel solution processable ultrahigh RI material (n = 2.50), which can be casted into homogeneous thin films using wet-chemical deposition methods. Owing to its 2D morphology, thin films of LTS nanosheets are able to swell in response to changes of relative humidity. Integration of LTS nanosheets into Bragg stacks (BSs) based on TiO2, SiO2, nanoparticles or H3Sb3P2O14 nanosheets affords multilayer systems with high optical quality at an extremely low device thickness of below 1 µm. Owing to the ultrahigh RI of LTS nanosheets and the high transparency of the thin films, BSs based on porous titania as the low-RI material are realized for the first time, showing potential application in light-managing devices. Moreover, the highest RI contrast ever realized in BSs based on SiO2 and LTS nanosheets is reported. Finally, exceptional swelling capability of an all-nanosheet BS based on LTS and H3Sb3P2O14 nanosheets is demonstrated, which bodes well for a new generation of humidity sensors with extremely high sensitivity.

This study presents a simple method that allows us to modify the composition, morphological, and surface properties of three-dimensional hierarchical Nb3O7(OH) superstructures, resulting in strongly enhanced photocatalytic H2 production. The superstructures consist of highly ordered nanowire networks and self-assemble under hydrothermal conditions. The presence of titanium affects the morphology of the superstructures, resulting in increased surface areas for higher doping levels. Up to 12 at. % titanium is incorporated into the Nb3O7(OH) crystal lattice via substitution of niobium at its octahedral lattice sites. Further titanium excess results in the formation of niobium-doped TiO2 plates, which overgrow the surface of the Nb3O7(OH) superstructures. Photoluminescence spectroscopy indicates fewer charge recombination processes near the surface of the nanostructures with an increasing titanium concentration in the crystal lattice. The combination of larger surface areas with fewer quenching sites at the crystal surface yields higher H2 evolution rates for the doped samples, with the rate being doubled by incorporation of 5.5 ± 0.7 at. % Ti.

While considerable efforts have been devoted to developing functionalized covalent organic frameworks (COFs) as oxygen evolution electrocatalysts in recent years, studies related to the investigation of the true catalytically active species for the oxygen evolution reaction (OER) remain lacking in the field. In this work, the active species of a cobalt-functionalized COF (TpBpy-Co) is studied as electrochemical OER catalyst through a series of electrochemical measurements and post-electrolysis characterizations. These results suggest that cobalt oxide-based nanoparticles are formed in TpBpy-Co from Co(II) ions coordinated to the COF backbone when exposing TpBpy-Co to alkaline media, and these newly formed nanoparticles serve as the primary active species for oxygen evolution. The study thus emphasizes that caution is warranted when assessing the catalytic activity of COF electrocatalysts, as the pristine COF may act as the pre-catalyst, with the active species forming only under catalyst operating conditions. Specifically, strong coordination between COFs and metal centers under electrochemical operation conditions is crucial to avoid unintended transformation of COF electrocatalysts. This work thus contributes to the rational development of earth-abundant COF OER catalysts for the production of green hydrogen from renewable resources., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Next-generation light-emitting applications such as displays and optical communications require judicious control over emitted light, including intensity and angular dispersion. To date, this remains a challenge as conventional methods require cumbersome optics. Here, we report highly directional and enhanced electroluminescence from a solution-processed quasi-2-dimensional halide perovskite light-emitting diode by building a device architecture to exploit hybrid plasmonic-photonic Tamm plasmon modes. By exploiting the processing and bandgap tunability of the halide perovskite device layers, we construct the device stack to optimise both optical and charge-injection properties, leading to narrow forward electroluminescence with an angular full-width half-maximum of 36.6° compared with the conventional isotropic control device of 143.9°, and narrow electroluminescence spectral full-width half-maximum of 12.1 nm. The device design is versatile and tunable to work with emission lines covering the visible spectrum with desired directionality, thus providing a promising route to modular, inexpensive, and directional operating light-emitting devices., (© 2024. The Author(s).)

Although sensor technologies have allowed us to outperform the human senses of sight, hearing, and touch, the development of artificial noses is significantly behind their biological counterparts. This largely stems from the sophistication of natural olfaction, which relies on both fluid dynamics within the nasal anatomy and the response patterns of hundreds to thousands of unique molecular-scale receptors. We designed a sensing approach to identify volatiles inspired by the fluid dynamics of the nose, allowing us to extract information from a single sensor (here, the reflectance spectra from a mesoporous one-dimensional photonic crystal) rather than relying on a large sensor array. By accentuating differences in the nonequilibrium mass-transport dynamics of vapors and training a machine learning algorithm on the sensor output, we clearly identified polar and nonpolar volatile compounds, determined the mixing ratios of binary mixtures, and accurately predicted the boiling point, flash point, vapor pressure, and viscosity of a number of volatile liquids, including several that had not been used for training the model. We further implemented a bioinspired active sniffing approach, in which the analyte delivery was performed in well-controlled 'inhale-exhale' sequences, enabling an additional modality of differentiation and reducing the duration of data collection and analysis to seconds. Our results outline a strategy to build accurate and rapid artificial noses for volatile compounds that can provide useful information such as the composition and physical properties of chemicals, and can be applied in a variety of fields, including disease diagnosis, hazardous waste management, and healthy building monitoring.

Due to the novel properties of both 2D materials and rare-earth elements, developing 2D rare-earth nanomaterials has a growing interest in research. To produce the most efficient rare-earth nanosheets, it is essential to find out the correlation between chemical composition, atomic structure and luminescent properties of individual sheets. In this study, 2D nanosheets exfoliated from Pr 3+ -doped KCa 2 Nb 3 O 10 particles with different Pr concentrations were investigated. Energy dispersive X-ray spectroscopy analysis indicates that the nanosheets contain Ca, Nb and O and a varying Pr content between 0.9 and 1.8 at%. K was completely removed after exfoliation. The crystal structure is monoclinic as in the bulk. The thinnest nanosheets are 3 nm corresponding to one triple perovskite-type layer with Nb on the B sites and Ca on the A sites, surrounded by charge compensating TBA + molecules. Thicker nanosheets of 12 nm thickness (and above) were observed too by transmission electron microscopy with the same chemical composition. This indicates that several perovskite-type triple layers remain stacked similar to the bulk. Luminescent properties of individual 2D nanosheets were studied using a cathodoluminescence spectrometer revealing additional transitions in the visible region in comparison to the spectra of different bulk phases., (© 2023. The Author(s).)

The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host-guest phenomena in well-defined 3D solid materials. In this work, we detail the synthesis of a diamine-based light-driven molecular motor and its incorporation into a series of imine-based polymers and covalent organic frameworks (COF). We study structural and dynamic properties of the molecular building blocks and derived self-assembled solids with a series of spectroscopic, diffraction, and theoretical methods. Using an acid-catalyzed synthesis approach, we are able to obtain the first crystalline 2D COF with stacked hexagonal layers that contains 20 mol% molecular motors. The COF features a specific pore volume and surface area of up to 0.45 cm 3 g -1 and 604 m 2 g -1 , respectively. Given the molecular structure and bulkiness of the diamine motor, we study the supramolecular assembly of the COF layers and detail stacking disorders between adjacent layers. We finally probe the motor dynamics with in situ spectroscopic techniques revealing current limitations in the analysis of these new materials and derive important analysis and design criteria as well as synthetic access to new generations of motorized porous framework materials., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

The in-depth understanding of the reported photoelectrochemical properties of the layered carbon nitride, poly(triazine imide)/LiCl (PTI/LiCl), has been limited by the apparent disorder of the Li/H atoms within its framework. To understand and resolve the current structural ambiguities, an optimized one-step flux synthesis (470 °C, 36 h, LiCl/KCl flux) was used to prepare PTI/LiCl and deuterated-PTI/LiCl in high purity. Its structure was characterized by a combination of neutron/X-ray diffraction and transmission electron microscopy. The range of possible Li/H atomic configurations was enumerated for the first time and, combined with total energy calculations, reveals a more complex energetic landscape than previously considered. Experimental data were fitted against all possible structural models, exhibiting the most consistency with a new orthorhombic model (Sp. Grp. Ama 2) that also has the lowest total energy. In addition, a new Cu(i)-containing PTI (PTI/CuCl) was prepared with the more strongly scattering Cu(i) cations in place of Li, and most closely matching with the partially-disorder structure in Cmc 2 1 . Thus, a complex configurational landscape of PTI is revealed to consist of a number of ordered crystalline structures that are new potential synthetic targets, such as with the use of metal-exchange reactions., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Covalent organic frameworks (COFs) offer a number of key properties that predestine them to be used as heterogeneous photocatalysts, including intrinsic porosity, long-range order, and light absorption. Since COFs can be constructed from a practically unlimited library of organic building blocks, these properties can be precisely tuned by choosing suitable linkers. Herein, we report the construction and use of a novel COF (FEAx-COF) photocatalyst, inspired by natural flavin cofactors. We show that the functionality of the alloxazine chromophore incorporated into the COF backbone is retained and study the effects of this heterogenization approach by comparison with similar molecular photocatalysts. We find that the integration of alloxazine chromophores into the framework significantly extends the absorption spectrum into the visible range, allowing for photocatalytic oxidation of benzylic alcohols to aldehydes even with low-energy visible light. In addition, the activity of the heterogeneous COF photocatalyst is less dependent on the chosen solvent, making it more versatile compared to molecular alloxazines. Finally, the use of oxygen as the terminal oxidant renders FEAx-COF a promising and "green" heterogeneous photocatalyst., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

α-RuCl 3 is a major candidate for the realization of the Kitaev quantum spin liquid, but its zigzag antiferromagnetic order at low temperatures indicates deviations from the Kitaev model. We have quantified the spin Hamiltonian of α-RuCl 3 by a resonant inelastic x-ray scattering study at the Ru L 3 absorption edge. In the paramagnetic state, the quasi-elastic intensity of magnetic excitations has a broad maximum around the zone center without any local maxima at the zigzag magnetic Bragg wavevectors. This finding implies that the zigzag order is fragile and readily destabilized by competing ferromagnetic correlations. The classical ground state of the experimentally determined Hamiltonian is actually ferromagnetic. The zigzag state is stabilized by quantum fluctuations, leaving ferromagnetism - along with the Kitaev spin liquid - as energetically proximate metastable states. The three closely competing states and their collective excitations hold the key to the theoretical understanding of the unusual properties of α-RuCl 3 in magnetic fields., (© 2021. The Author(s).)

Porphyrin-based metal-organic frameworks (MOFs), exemplified by MOF-525, PCN-221, and PCN-224, are promising systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, based on a comprehensive synthetic and structural analysis spanning local and long-range length scales, we show that PCN-221 consists of Zr 6 O 4 (OH) 4 clusters in four distinct orientations within the unit cell, rather than Zr 8 O 6 clusters as originally published, and linker vacancies at levels of around 50%, which may form in a locally correlated manner. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster-linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.

Controlling autonomous propulsion of microswimmers is essential for targeted drug delivery and applications of micro/nanomachines in environmental remediation and beyond. Herein, we report two-dimensional (2D) carbon nitride-based Janus particles as highly efficient, light-driven microswimmers in aqueous media. Due to the superior photocatalytic properties of poly(heptazine imide) (PHI), the microswimmers are activated by both visible and ultraviolet (UV) light in conjunction with different capping materials (Au, Pt, and SiO 2 ) and fuels (H 2 O 2 and alcohols). Assisted by photoelectrochemical analysis of the PHI surface photoreactions, we elucidate the dominantly diffusiophoretic propulsion mechanism and establish the oxygen reduction reaction (ORR) as the major surface reaction in ambient conditions on metal-capped PHI and even with TiO 2 -based systems, rather than the hydrogen evolution reaction (HER), which is generally invoked as the source of propulsion under ambient conditions with alcohols as fuels. Making use of the intrinsic solar energy storage ability of PHI, we establish the concept of photocapacitive Janus microswimmers that can be charged by solar energy, thus enabling persistent light-induced propulsion even in the absence of illumination-a process we call "solar battery swimming"-lasting half an hour and possibly beyond. We anticipate that this propulsion scheme significantly extends the capabilities in targeted cargo/drug delivery, environmental remediation, and other potential applications of micro/nanomachines, where the use of versatile earth-abundant materials is a key prerequisite., Competing Interests: The authors declare no competing interest., (Copyright © 2020 the Author(s). Published by PNAS.)

Two-dimensional (2D) polymers hold great promise in the rational materials design tailored for next-generation applications. However, little is known about the grain boundaries in 2D polymers, not to mention their formation mechanisms and potential influences on the material's functionalities. Using aberration-corrected high-resolution transmission electron microscopy, we present a direct observation of the grain boundaries in a layer-stacked 2D polyimine with a resolution of 2.3 Å, shedding light on their formation mechanisms. We found that the polyimine growth followed a "birth-and-spread" mechanism. Antiphase boundaries implemented a self-correction to the missing-linker and missing-node defects, and tilt boundaries were formed via grain coalescence. Notably, we identified grain boundary reconstructions featuring closed rings at tilt boundaries. Quantum mechanical calculations revealed that boundary reconstruction is energetically allowed and can be generalized into different 2D polymer systems. We envisage that these results may open up the opportunity for future investigations on defect-property correlations in 2D polymers., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Quantitative comparison of photocatalytic performances across different photocatalysis setups is technically challenging. Here, we combine the concepts of relative and optimal photonic efficiencies to normalize activities with an internal benchmark material, RuO 2 photodeposited on a P25-TiO 2 photocatalyst, which was optimized for reproducibility of the oxygen evolution reaction (OER). Additionally, a general set of good practices was identified to ensure reliable quantification of photocatalytic OER, including photoreactor design, photocatalyst dispersion, and control of parasitic reactions caused by the sacrificial electron acceptor. Moreover, a method combining optical modeling and measurements was proposed to quantify the benchmark absorbed and scattered light (7.6% and 81.2%, respectively, of λ  = 300-500 nm incident photons), rather than just incident light (≈AM 1.5G), to estimate its internal quantum efficiency (16%). We advocate the adoption of the instrumental and theoretical framework provided here to facilitate material standardization and comparison in the field of artificial photosynthesis., Competing Interests: The authors declare no competing interests., (© 2020 The Authors.)

Interactions between extended π-systems are often invoked as the main driving force for stacking and crystallization of 2D organic polymers. In covalent organic frameworks (COFs), the stacking strongly influences properties such as the accessibility of functional sites, pore geometry, and surface states, but the exact nature of the interlayer interactions is mostly elusive. The stacking mode is often identified as eclipsed based on observed high symmetry diffraction patterns. However, as pointed out by various studies, the energetics of eclipsed stacking are not favorable and offset stacking is preferred. This work presents lower and higher apparent symmetry modifications of the imine-linked TTI-COF prepared through high- and low-temperature reactions. Through local structure investigation by pair distribution function analysis and simulations of stacking disorder, we observe random local layer offsets in the low temperature modification. We show that while stacking disorder can be easily overlooked due to the apparent crystallographic symmetry of these materials, total scattering methods can help clarify this information and suggest that defective local structures could be much more prevalent in COFs than previously thought. A detailed analysis of the local structure helps to improve the search for and design of highly porous tailor-made materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The rational design of high performance sodium solid electrolytes is one of the key challenges in modern battery research. In this work, we identify new sodium ion conductors in the substitution series Na 5- x Al 1- x Si x S4 (0 ≤ x ≤ 1), which are entirely based on earth-abundant elements. These compounds exhibit conductivities ranging from 1.64 · 10 -7 for Na 4 SiS 4 to 2.04 · 10 -5 for Na 8.5 (AlS 4 ) 0.5 (SiS 4 ) 1.5 ( x = 0.75). We determined the crystal structures of the Na + -ion conductors Na 4 SiS 4 as well as hitherto unknown Na 5 AlS 4 and Na 9 (AlS 4 )(SiS 4 ). Na + -ion conduction pathways were calculated by bond valence energy landscape (BVEL) calculations for all new structures highlighting the influence of the local coordination symmetry of sodium ions on the energy landscape within this family. Our findings show that the interplay of charge carrier concentration and low site symmetry of sodium ions can enhance the conductivity by several orders of magnitude., (Copyright © 2020 Harm, Hatz, Schneider, Hoefer, Hoch and Lotsch.)

Covalent organic frameworks (COFs) are typically designed by breaking down the desired network into feasible building blocks - either simple and highly symmetric, or more convoluted and thus less symmetric. The linkers are chosen complementary to each other such that an extended, fully condensed network structure can form. We show not only an exception, but a design principle that allows breaking free of such design rules. We show that tri- and tetratopic linkers can be combined to form imine-linked [4 + 3] sub-stoichiometric 2D COFs featuring an unexpected bex net topology, and with periodic uncondensed amine functionalities which enhance CO 2 adsorption, can be derivatized in a subsequent reaction, and can also act as organocatalysts. We further extend this class of nets by including a ditopic linker to form [4 + 3 + 2] COFs. The results open up possibilities towards a new class of sub-valent COFs with unique structural, topological and compositional complexities for diverse applications.

Stabilization of covalent organic frameworks (COFs) by post-synthetic locking strategies is a powerful tool to push the limits of COF utilization, which are imposed by the reversible COF linkage. Here we introduce a sulfur-assisted chemical conversion of a two-dimensional imine-linked COF into a thiazole-linked COF, with full retention of crystallinity and porosity. This post-synthetic modification entails significantly enhanced chemical and electron beam stability, enabling investigation of the real framework structure at a high level of detail. An in-depth study by electron diffraction and transmission electron microscopy reveals a myriad of previously unknown or unverified structural features such as grain boundaries and edge dislocations, which are likely generic to the in-plane structure of 2D COFs. The visualization of such real structural features is key to understand, design and control structure-property relationships in COFs, which can have major implications for adsorption, catalytic, and transport properties of such crystalline porous polymers.

Recent interest in topological semimetals has led to the proposal of many new topological phases that can be realized in real materials. Next to Dirac and Weyl systems, these include more exotic phases based on manifold band degeneracies in the bulk electronic structure. The exotic states in topological semimetals are usually protected by some sort of crystal symmetry, and the introduction of magnetic order can influence these states by breaking time-reversal symmetry. We show that we can realize a rich variety of different topological semimetal states in a single material, CeSbTe. This compound can exhibit different types of magnetic order that can be accessed easily by applying a small field. Therefore, it allows for tuning the electronic structure and can drive it through a manifold of topologically distinct phases, such as the first nonsymmorphic magnetic topological phase with an eightfold band crossing at a high-symmetry point. Our experimental results are backed by a full magnetic group theory analysis and ab initio calculations. This discovery introduces a realistic and promising platform for studying the interplay of magnetism and topology. We also show that we can generally expand the numbers of space groups that allow for high-order band degeneracies by introducing antiferromagnetic order.

The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant 'defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts.

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra-high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond-shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two-dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac nodes.

Hydrogen evolution from photocatalytic reduction of water holds promise as a sustainable source of carbon-free energy. Covalent organic frameworks (COFs) present an interesting new class of photoactive materials, which combine three key features relevant to the photocatalytic process, namely crystallinity, porosity and tunability. Here we synthesize a series of water- and photostable 2D azine-linked COFs from hydrazine and triphenylarene aldehydes with varying number of nitrogen atoms. The electronic and steric variations in the precursors are transferred to the resulting frameworks, thus leading to a progressively enhanced light-induced hydrogen evolution with increasing nitrogen content in the frameworks. Our results demonstrate that by the rational design of COFs on a molecular level, it is possible to precisely adjust their structural and optoelectronic properties, thus resulting in enhanced photocatalytic activities. This is expected to spur further interest in these photofunctional frameworks where rational supramolecular engineering may lead to new material applications.

The reorientational dynamics of ammonium dicyanamide ND4[N(C[triple bond]N)2] and the kinetics as well as the mechanism of the solid-state isomerization reaction from ammonium dicyanamide into dicyandiamide (N[triple bond]C-N==C(NH2)2) was studied by means of 2H and 14N solid-state NMR spectroscopy in a temperature range between 38 and 390 K. Whereas in previous investigations the mechanism of the solid-state transformation was investigated by means of vibrational and magic angle spinning solid-state NMR spectroscopy as well as neutron diffraction, we here present a comprehensive 2H study of the ammonium ion dynamics prior to and during the course of the reaction, thereby highlighting possible cross correlations between dynamics and reactivity involving the ammonium ion. The ND4+ group was found to undergo thermally activated random jumps in a tetrahedral potential, which is increasingly distorted with increasing temperature, giving rise to an asymmetrically compressed or elongated tetrahedron with deviations from the tetrahedral angle of up to 6 degrees . The correlation time follows an Arrhenius law with an activation energy of Ea = 25.8(2) kJ mol(-1) and an attempt frequency of tau0(-1) = 440(80) THz. The spin-lattice relaxation times were fitted according to a simple Bloembergen-Purcell-Pound type model with a T1 minimum of 4 ms at 230 K. Temperature-dependent librational amplitudes were extracted by line-shape simulations between 38 and 390 K and contrasted with those obtained by neutron diffraction, their values ranging between 5 and 28 degrees . The onset and progress of the solid-phase transformation were followed in situ at temperatures above 372 K and could be classified as a strongly temperature-dependent, heterogeneous two-step reaction proceeding with rapid evolution of ammonia and comparatively slow subsequent reintegration into the solid. On the microscopic level, this correlates with a rapid proton transfer -- possibly triggered by a coupling between the ammonium ion dynamics and phonon modes on the terahertz time scale -- and an essentially decoupled nucleophilic attack of ammonia at the nitrile carbon, giving rise to significantly differing time constants for the two processes.