Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Tailoring C─N Containing Compounds into Carbon Nanomaterials with Tunable Morphologies for Electrocatalytic Applications.

Carbon materials with unique sp2 -hybridization are extensively researched for catalytic applications due to their excellent conductivity and tunable physicochemical properties. However, the development of economic approaches to tailoring carbon materials into desired morphologies remains a challenge. Herein, a convenient "bottom-up" strategy by pyrolysis of graphitic carbon nitride (g-C3 N4 ) (or other carbon/nitrogen (C, N)-enriched compounds) together with selected metal salts and molecules is reported for the construction of different carbon-based catalysts with tunable morphologies, including carbon nano-balls, carbon nanotubes, nitrogen/sulfur (S, N) doped-carbon nanosheets, and single-atom catalysts, supported by carbon layers. The catalysts are systematically investigated through various microscopic, spectroscopic, and diffraction methods and they demonstrate promising and broad applications in electrocatalysis such as in the oxygen reduction reaction and water splitting. Mechanistic monitoring of the synthesis process through online thermogravimetric-gas chromatography-mass spectrometry measurements indicates that the release of C─N-related moieties, such as dicyan, plays a key role in the growth of carbon products. This enables to successfully predict other widely available precursor compounds beyond g-C3 N4 such as caffeine, melamine, and urea. This work develops a novel and economic strategy to generate morphologically diverse carbon-based catalysts and provides new, essential insights into the growth mechanism of carbon nanomaterials syntheses.

Synergy of dual-atom catalysts deviated from the scaling relationship for oxygen evolution reaction.

Dual-atom catalysts, particularly those with heteronuclear active sites, have the potential to outperform the well-established single-atom catalysts for oxygen evolution reaction, but the underlying mechanistic understanding is still lacking. Herein, a large-scale density functional theory is employed to explore the feasibility of *O-*O coupling mechanism, which can circumvent the scaling relationship with improving the catalytic performance of N-doped graphene supported Fe-, Co-, Ni-, and Cu-containing heteronuclear dual-atom catalysts, namely, M'M@NC. Based on the constructed activity maps, a rationally designed descriptor can be obtained to predict homonuclear catalysts. Seven heteronuclear and four homonuclear dual-atom catalysts possess high activities that outperform the minimum theoretical overpotential. The chemical and structural origin in favor of *O-*O coupling mechanism thus leading to enhanced reaction activity have been revealed. This work not only provides additional insights into the fundamental understanding of reaction mechanisms, but also offers a guideline for the accelerated discovery of efficient catalysts.

Optimized NiFe-Based Coordination Polymer Catalysts: Sulfur-Tuning and Operando Monitoring of Water Oxidation.

In-depth insights into the structure-activity relationships and complex reaction mechanisms of oxygen evolution reaction (OER) electrocatalysts are indispensable to efficiently generate clean hydrogen through water electrolysis. We introduce a convenient and effective sulfur heteroatom tuning strategy to optimize the performance of active Ni and Fe centers embedded into coordination polymer (CP) catalysts. Operando monitoring then provided the mechanistic understanding as to how exactly our facile sulfur engineering of Ni/Fe-CPs optimizes the local electronic structure of their active centers to facilitate dioxygen formation. The high OER activity of our optimized S-R-NiFe-CPs outperforms the most recent NiFe-based OER electrocatalysts. Specifically, we start from oxygen-deprived Od-R-NiFe-CPs and transform them into highly active Ni/Fe-CPs with tailored sulfur coordination environments and anionic deficiencies. Our operando X-ray absorption spectroscopy analyses reveal that sulfur introduction into our designed S-R-NiFe-CPs facilitates the formation of crucial highly oxidized Ni4+ and Fe4+ species, which generate oxygen-bridged NiIV-O-FeIV moieties that act as the true OER active intermediates. The advantage of our sulfur-doping strategy for enhanced OER is evident from comparison with sulfur-free Od-R-NiFe-CPs, where the formation of essential high-valent OER intermediates is hindered. Moreover, we propose a dual-site mechanism pathway, which is backed up with a combination of pH-dependent performance data and DFT calculations. Computational results support the benefits of sulfur modulation, where a lower energy barrier enables O-O bond formation atop the S-NiIV-O-FeIV-O moieties. Our convenient anionic tuning strategy facilitates the formation of active oxygen-bridged metal motifs and can thus promote the design of flexible and low-cost OER electrocatalysts.

Dynamics and control of active sites in hierarchically nanostructured cobalt phosphide/chalcogenide-based electrocatalysts for water splitting.

The rational design of efficient electrocatalysts for industrial water splitting is essential to generate sustainable hydrogen fuel. However, a comprehensive understanding of the complex catalytic mechanisms under harsh reaction conditions remains a major challenge. We apply a self-templated strategy to introduce hierarchically nanostructured "all-surface" Fe-doped cobalt phosphide nanoboxes (Co@CoFe-P NBs) as alternative electrocatalysts for industrial-scale applications. Operando Raman spectroscopy and X-ray absorption spectroscopy (XAS) experiments were carried out to track the dynamics of their structural reconstruction and the real catalytically active intermediates during water splitting. Our operando analyses reveal that partial Fe substitution in cobalt phosphides promotes a structural reconstruction into P-Co-O-Fe-P configurations with low-valence metal centers (M0/M+) during the hydrogen evolution reaction (HER). Results from density functional theory (DFT) demonstrate that these in situ reconstructed configurations significantly enhance the HER performance by lowering the energy barrier for water dissociation and by facilitating the adsorption/desorption of HER intermediates (H*). The competitive activity in the oxygen evolution reaction (OER) arises from the transformation of the reconstructed P-Co-O-Fe-P configurations into oxygen-bridged, high-valence CoIV-O-FeIV moieties as true active intermediates. In sharp contrast, the formation of such CoIII/IV-O-FeIII/IV moieties in Co-FeOOH is hindered under the same conditions, which outlines the key advantages of phosphide-based electrocatalysts. Ex situ studies of the as-synthesized reference cobalt sulfides (Co-S), Fe doped cobalt selenides (Co@CoFe-Se), and Fe doped cobalt tellurides (Co@CoFe-Te) further corroborate the observed structural transformations. These insights are vital to systematically exploit the intrinsic catalytic mechanisms of non-oxide, low-cost, and robust overall water splitting electrocatalysts for future energy conversion and storage.

Mechanistic insight into the active centers of single/dual-atom Ni/Fe-based oxygen electrocatalysts.

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm-2. We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O2 atop the Ni-O-Fe sites.

Reaction kinetics and interplay of two different surface states on hematite photoanodes for water oxidation.

Understanding the function of surface states on photoanodes is crucial for unraveling the underlying reaction mechanisms of water oxidation. For hematite photoanodes, only one type of surface states with higher oxidative energy (S1) has been proposed and verified as reaction intermediate, while the other surface state located at lower potentials (S2) was assigned to inactive or recombination sites. Through employing rate law analyses and systematical (photo)electrochemical characterizations, here we show that S2 is an active reaction intermediate for water oxidation as well. Furthermore, we demonstrate that the reaction kinetics and dynamic interactions of both S1 and S2 depend significantly on operational parameters, such as illumination intensity, nature of the electrolyte, and applied potential. These insights into the individual reaction kinetics and the interplay of both surface states are decisive for designing efficient photoanodes.

Bifunctional Single Atom Electrocatalysts: Coordination-Performance Correlations and Reaction Pathways.

Single atom catalysts (SACs) are ideal model systems in catalysis research. Here we employ SACs to address the fundamental catalytic challenge of generating well-defined active metal centers to elucidate their interactions with coordinating atoms, which define their catalytic performance. We introduce a soft-landing molecular strategy for tailored SACs based on metal phthalocyanines (MPcs, M = Ni, Co, Fe) on graphene oxide (GO) layers to generate well-defined model targets for mechanistic studies. The formation of electronic channels through π-π conjugation with the graphene sheets enhances the MPc-GO performance in both oxygen evolution and reduction reactions (OER and ORR). Density functional theory (DFT) calculations unravel that the outstanding ORR activity of FePc-GO among the series is due to the high affinity of Fe atoms toward O2 species. Operando X-ray absorption spectroscopy and DFT studies demonstrate that the OER performance of the catalysts relates to thermodynamic or kinetic control at low- or high-potential ranges, respectively. We furthermore provide evidence that the participation of ligating N and C atoms around the metal centers provides a wider selection of active OER sites for both NiPc-GO and CoPc-GO. Our strategy promotes the understanding of coordination-activity relationships of high-performance SACs and their optimization for different processes through tailored combinations of metal centers and suitable ligand environments.

Dynamic Role of Cluster Cocatalysts on Molecular Photoanodes for Water Oxidation.

While loading of cocatalysts is one of the most widely investigated strategies to promote the efficiency of photoelectrodes, the understanding of their functionality remains controversial. We established new hybrid molecular photoanodes with cobalt-based molecular cubane cocatalysts on hematite as a model system. Photoelectrochemical and rate law analyses revealed an interesting functionality transition of the {Co(II)4O4}-type cocatalysts. Their role changed from predominant hole reservoirs to catalytic centers upon modulation of the applied bias. Kinetic analysis of the photoelectrochemical processes indicated that this observed transition arises from the dynamic equilibria of photogenerated surface charge carriers. Most importantly, we confirmed this functional transition of the cocatalysts and the related kinetic properties for several cobalt-based molecular and heterogeneous catalysts, indicating wide applicability of the derived trends. Additionally, complementary analytical characterizations show that a transformation of the applied molecular species occurs at higher applied bias, pointing to a dynamic interplay connecting molecular and heterogeneous catalysis. Our insights promote the essential understanding of efficient (molecular) cocatalyzed photoelectrode systems to design tailor-made hybrid devices for a wide range of catalytic applications.

Compressible and Recyclable Monolithic g-C3N4/Melamine Sponge: A Facile Ultrasonic-Coating Approach and Enhanced Visible-Light Photocatalytic Activity.

Powdery photocatalysts seriously restrict their practical application due to the difficult recycle and low photocatalytic activity. In this work, a monolithic g-C3N4/melamine sponge (g-C3N4/MS) was successfully fabricated by a cost-effective ultrasonic-coating route, which is easy to achieve the uniform dispersion and firm loading of g-C3N4 on MS skeleton. The monolithic g-C3N4/MS entirely inherits the porous structure of MS and results in a larger specific surface area (SSA) than its powdery counterpart. Benefit from this monolithic structure, g-C3N4/MS gains more exposed active sites, enhanced visible-light absorption and separation of photogenerated carriers, thus achieving noticeable photocatalytic activity on nitric oxide (NO) removal and CO2 reduction. Specifically, NO removal ratio is as high as 78.6% which is 4.5 times higher than that of the powdery g-C3N4, and yield rate of CO and CH4 attains 7.48 and 3.93 µmol g-1 h-1. Importantly, the features of low-density, high porosity, good elasticity, and firmness, not only endow g-C3N4/MS with flexibility in various environmental applications, but also make it easy to recycle and stable for long-time application. Our work provides a feasible approach to fabricate novel monolithic photocatalysts with large-scale production and application.

A mathematical model of bowel sound generation.

Humans have been interested in bowel sounds and wondered about their origins for millennia. To better understand the phenomenon, a mathematical model of bowel sound generation was developed based on a spring-mass-damping system. This is similar to vocal folds models for speech. The bowel sound model has four parameters that link to bowel activities: the individual wave component, pressure index, component quantity, and component interval time. All types of bowel sound documented previously can be modelled by combining different values for these parameters. Further, a 2500 ms bowel sound incorporating all the common types was simulated to present the model's accuracy.