Pyrolysis Free Out-of-Plane Co-Single Atomic Sites in Porous Organic Photopolymer Stimulates Solar-Powered CO2 Fixation.

Herein, a facile strategy is illustrated to develop pyrolysis-free out-of-plane coordinated single atomic sites-based M-POP via a one-pot Friedel Craft acylation route followed by a post-synthetic metalation. The optimized geometry of the Co@BiPy-POP clearly reveals the presence of out-of-plane Co-single atomic sites in the porous backbone. This novel photopolymer Co@BiPy-POP shows extensive π-conjugations followed by impressive light harvesting ability and is utilized for photochemical CO2 fixation to value-added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert-butyl ammonium bromide (TBAB). Synchrotron-based X-ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis-free out-of-plane-coordination strategy and further explores the role of single atomic sites in carrying out feasible CO2 fixation reactions.

Distortion-Induced Interfacial Charge Transfer at Single Cobalt Atom Secured on Ordered Intermetallic Surface Enhances Pure Oxygen Production.

In this work, atomic cobalt (Co) incorporation into the Pd2Ge intermetallic lattice facilitates operando generation of a thin layer of CoO over Co-substituted Pd2Ge, with Co in the CoO surface layer functioning as single metal sites. Hence the catalyst has been titled Co1-CoO-Pd2Ge. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm the existence of CoO, with some of the Co bonded to Ge by substitution of Pd sites in the Pd2Ge lattice. The role of the CoO layer in the oxygen evolution reaction (OER) has been verified by its selective removal using argon sputtering and conducting the OER on the etched catalyst. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy demonstrate that CoO gets transformed to CoOOH (Co3+) in operando condition with faster charge transfer through Pd atoms in the core Pd2Ge lattice. In situ Raman spectroscopy depicts the emergence of a CoOOH phase on applying potential and shows that the phase is stable with increasing potential and time without getting converted to CoO2. Density functional theory calculations indicate that the Pd2Ge lattice induces distortion in the CoO phase and generates unpaired spins in a nonmagnetic CoOOH system resulting in an increase in the OER activity and durability. The existence of spin density even after electrocatalysis is verified from electron paramagnetic resonance spectroscopy. We have thus successfully synthesized intermetallic supported CoO during synthesis and rigorously verified the role played by an intermetallic Pd2Ge core in enhancing charge transfer, generating spin density, improving electrochemical durability, and imparting mechanical stability to a thin CoOOH overlayer. Differential electrochemical mass spectrometry has been explored to visualize the instantaneous generation of oxygen gas during the onset of the reaction.

Tweaking Photo CO2 Reduction by Altering Lewis Acidic Sites in Metalated-Porous Organic Polymer for Adjustable H2 /CO Ratio in Syngas Production.

Herein, we have specifically designed two metalated porous organic polymers (Zn-POP and Co-POP) for syngas (CO+H2 ) production from gaseous CO2 . The variable H2 /CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO2 reduction and water splitting with the help of the two catalysts, where CO (145.65 µmol g-1 h-1 ) and H2 (434.7 µmol g-1 h-1 ) production were preferentially obtained over Co-POP & Zn-POP, respectively. The higher electron density/better Lewis basic nature of Co-POP was investigated further using XPS, XANES, and NH3 -TPD studies, which considerably improve CO2 activation capacity. Moreover, the structure-activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO2 reduction over Co-POP while water splitting occurred preferentially over Zn-POP.

Highly Efficient Electrochemical Hydrogen Evolution with Ultra-Low Loading of Strongly Adhered Pt Nanoparticles on Carbon.

The development of robust electrocatalysts with low platinum content for acidic hydrogen evolution reaction (HER) is paramount for large scale commercialization of proton exchange membrane electrolyzers. Herein, a simple strategy is reported to synthesize a well anchored, low Pt containing Vulcan carbon catalyst using ZnO as a sacrificial template. Pt containing ZnO (PZ) is prepared by a simultaneous borohydride reduction. PZ is then loaded onto Vulcan carbon to produce a very low Pt content electrocatalyst, PZ@VC. PZ@VC with 2 wt.% Pt shows excellent performance for acidic HER in comparison to the commercial Pt/C (20 wt.%) catalyst. PZ@VC with a very low Pt loading shows significantly low η10 and η100 values (15 and 46 mV, respectively). PZ@VC on coating with Nafion (PZ@VC-N) shows further improvement in its performance (η10 of 7 mV, η100 of 28 mV) with ≈300 h of stability (≈10 mA cm-2 ) with only 4 µgPt cm-2 . PZ@VC-N shows a record high mass activity of 71 A mgPt -1 (32 times larger than Pt/C (20 wt.%) at 50 mV of overpotential. Post reaction characterizations reveal Pt nanoparticles are embedded onto VC with no traces of zinc, suggestive of a strong metal-support interaction leading to this high stability at low Pt loading.

Cobalt-Induced Phase Transformation of Ni3Ga4 Generates Chiral Intermetallic Co3Ni3Ga8.

The scientific community has found immense difficulty to focus on the generation of chiral intermetallics compared to the chiral molecular structure, probably due to the technical difficulty in producing them as no general controlled protocol is available. Herein, using a conventional metal flux technique, we have discovered a new ternary intermetallic Co3Ni3Ga8, substituting Co at the Ni sublattice in a highly symmetric Ni3Ga4 (Ia3̅d). Co3Ni3Ga8 crystallizes in the I4132 space group, a Sohncke type, and can host the chiral structure. To the best of our knowledge, this is the first report of a ternary intermetallic crystallizing in this space group. The chiral structure of Co3Ni3Ga8 is comprehensively mapped by various techniques such as single-crystal X-ray diffraction (XRD), synchrotron powder XRD, X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM) and theoretically studied using density functional theory. The discovery of this chiral compound can inspire the researchers to design hidden ternary chiral intermetallics to study the exotic electrical and magnetic properties.

Wurtzite CuGaS2 with an In-Situ-Formed CuO Layer Photocatalyzes CO2 Conversion to Ethylene with High Selectivity.

We present surface reconstruction-induced C-C coupling whereby CO2 is converted into ethylene. The wurtzite phase of CuGaS2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO2 to ethylene (C2 H4 ). Upon illumination, the catalyst efficiently converts CO2 to C2 H4 with 75.1 % selectivity (92.7 % selectivity in terms of Relectron ) and a 20.6 µmol g-1 h-1 evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu2+ , with the assistance of existing Cu+ , functioning as an anchor for the generated *CO and thereby facilitating C-C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO2 reduction reaction pathway to selective formation of ethylene.

Intrinsic Charge Polarization in Bi19 S27 Cl3 Nanorods Promotes Selective CC Coupling Reaction during Photoreduction of CO2 to Ethanol.

Obtaining multi-carbon products via CO2  photoreduction is a major catalytic challenge involving multielectron-mediated CC bond formation. Complex design of multicomponent interfaces that are exploited to achieve this chemical transformation, often leads to untraceable deleterious changes in the interfacial chemical environment affecting CO2  conversion efficiency and product selectivity. Alternatively, robust metal centers having asymmetric charge distribution can effectuate CC coupling reaction through the stabilization of intermediates, for desired product selectivity. However, generating inherent charge distribution in a single component catalyst is a difficult material design challenge. Here, a novel photocatalyst, Bi19 S27 Cl3 , is presented which selectively converts CO2  to a C2  product, ethanol, in high yield under visible light irradiation. Structural analysis through transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy reveals the presence of charge polarized bismuth centers in Bi19 S27 Cl3 . The intrinsic electric field induced by charge polarized bismuth centers renders better separation efficiency of photogenerated electron-hole pair. Furthermore, charge polarized centers yield better adsorption of CO* intermediate and accelerate the rate determining CC coupling step through the formation of OCCOH intermediate. Formation of these intermediates is experimentally mapped by in situ Fourier-transform infrared spectroscopy and further confirmed by theoretical calculation.

Engineering the Charge Density on an In2.77S4/Porous Organic Polymer Hybrid Photocatalyst for CO2-to-Ethylene Conversion Reaction.

The development of an efficient photocatalyst for C2 product formation from CO2 is of urgent importance toward the deployment of solar-fuel production. Here, we report a template-free, cost-effective synthetic strategy to develop a carbazole-derived porous organic polymer (POP)-based composite catalyst. The composite catalyst is comprised of In2.77S4 and porous organic polymer (POP) and is held together by induced-polarity-driven electrostatic interaction. Utilizing the synergy of the catalytically active In centers and light-harvesting POPs, the catalyst showed 98.9% selectivity toward the generation of C2H4, with a formation rate of 67.65 µmol g-1 h-1. Two different oxidation states of the In2.77S4 spinel were exploited for the C-C coupling process, and this was investigated by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations. The role of POP was elucidated via several photophysical and photoelectrochemical studies. The electron transfer was mapped by several correlated approaches, which assisted in establishing the Z-scheme mechanism. Furthermore, the mechanism of C2H4 formation was extensively investigated using density functional theory (DFT) calculations from multiple possible pathways.

Improvement in Oxygen Evolution Performance of NiFe Layered Double Hydroxide Grown in the Presence of 1T-Rich MoS2.

NiFe layered double hydroxide (NiFe LDH) grown in the presence of MoS2 (rich in 1T phase) shows exceptional performance metrics for alkaline oxygen evolution reaction (OER) in this class of composites. The as-prepared NiFe LDH/MoS2 composite (abbreviated as MNF) exhibits a low overpotential (η10) of 190 mV; a low Tafel slope of 31 mV dec-1; and more importantly, a high stability in its performance manifested by the delivery of current output for 45 h. It is important to note that this could be achieved with an exceedingly low loading of 0.14 mg cm-2. The mass activity of this composite (97 A g-1) is about 14 times greater than that of the conventional RuO2 (7 A g-1) at η = 200 mV. When normalized with respect to the total metal content, a mass activity of 1000 A g-1 (η = 300 mV) was achieved. Impedance analysis further reveals that the significant reduction in charge-transfer resistance and hence high current density (5 times greater as compared to NiFe LDH at η = 300 mV) observed for MNF is associated with interfacial adsorption kinetics of intermediates (R1). Significant enhancement in the intrinsic activity of MNF over LDH has been observed through normalization of current with the electrochemically active surface area. Computational studies suggest that the Ni centers in the composite act as the active sites for OER, which is well-corroborated with the observed postreaction appearance of Ni3+ species.

In Situ Mechanistic Insights for the Oxygen Reduction Reaction in Chemically Modulated Ordered Intermetallic Catalyst Promoting Complete Electron Transfer.

The well-known limitation of alkaline fuel cells is the slack kinetics of the cathodic half-cell reaction, the oxygen reduction reaction (ORR). Platinum, being the most active ORR catalyst, is still facing challenges due to its corrosive nature and sluggish kinetics. Many novel approaches for substituting Pt have been reported, which suffer from stability issues even after mighty modifications. Designing an extremely stable, but unexplored ordered intermetallic structure, Pd2Ge, and tuning the electronic environment of the active sites by site-selective Pt substitution to overcome the hurdle of alkaline ORR is the main motive of this paper. The substitution of platinum atoms at a specific Pd position leads to Pt0.2Pd1.8Ge demonstrating a half-wave potential (E1/2) of 0.95 V vs RHE, which outperforms the state-of-the-art catalyst 20% Pt/C. The mass activity (MA) of Pt0.2Pd1.8Ge is 320 mA/mgPt, which is almost 3.2 times better than that of Pt/C. E1/2 and MA remained unaltered even after 50,000 accelerated degradation test (ADT) cycles, which makes it a promising stable catalyst with its activity better than that of the state-of-the-art Pt/C. The undesired 2e- transfer ORR forming hydrogen peroxide (H2O2) is diminished in Pt0.2Pd1.8Ge as visible from the rotating ring-disk electrode (RRDE) experiment, spectroscopically visualized by in situ Fourier transform infrared (FTIR) spectroscopy and supported by computational studies. The effect of Pt substitution on Pd has been properly manifested by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The swinging of the oxidation state of atomic sites of Pt0.2Pd1.8Ge during the reaction is probed by in situ XAS, which efficiently enhances 4e- transfer, producing an extremely low percentage of H2O2.

Activating oxygen deficient TiO2 in the visible region by Bi2MoO6 for CO2 photoreduction to methanol.

Fast photogenerated charge recombination and inappropriate bandgap for visible light driven charge generation hinders the performance of TiO2. In this study, TiO2 was activated for visible light driven CO2 reduction in the presence of Bi2MoO6 as an electron donor. Furthermore, the introduction of oxygen vacancies resulted in enhanced CO2 adsorption and conversion. The best catalyst gives 27.1 µmol g-1 h-1 methanol formation. DRIFTS was used to explain the methanol formation mechanism on oxygen deficient TiO2.

Morphology-Tuned Pt3 Ge Accelerates Water Dissociation to Industrial-Standard Hydrogen Production over a wide pH Range.

The discovery of novel materials for industrial-standard hydrogen production is the present need considering the global energy infrastructure. A novel electrocatalyst, Pt3 Ge, which is engineered with a desired crystallographic facet (202), accelerates hydrogen production by water electrolysis, and records industrially desired operational stability compared to the commercial catalyst platinum is introduced. Pt3 Ge-(202) exhibits low overpotential of 21.7 mV (24.6 mV for Pt/C) and 92 mV for 10 and 200 mA cm-2 current density, respectively in 0.5 m H2 SO4 . It also exhibits remarkable stability of 15 000 accelerated degradation tests cycles (5000 for Pt/C) and exceptional durability of 500 h (@10 mA cm-2 ) in acidic media. Pt3 Ge-(202) also displays low overpotential of 96 mV for 10 mA cm-2 current density in the alkaline medium, rationalizing its hydrogen production ability over a wide pH range required commercial operations. Long-term durability (>75 h in alkaline media) with the industrial level current density (>500 mA cm-2 ) has been demonstrated by utilizing the electrochemical flow reactor. The driving force behind this stupendous performance of Pt3 Ge-(202) has been envisaged by mapping the reaction mechanism, active sites, and charge-transfer kinetics via controlled electrochemical experiments, ex situ X-ray photoelectron spectroscopy, in situ infrared spectroscopy, and in situ X-ray absorption spectroscopy further corroborated by first principles calculations.

Potential- and Time-Dependent Dynamic Nature of an Oxide-Derived PdIn Nanocatalyst during Electrochemical CO2 Reduction.

Electrochemical reduction of CO2 into valuable fuels and chemicals is a promising route of replacing fossil fuels by reducing CO2 emissions and minimizing its adverse effects on the climate. Tremendous efforts have been carried out for designing efficient catalyst materials to selectively produce the desired product in high yield from CO2 by the electrochemical process. In this work, a strategy is reported to enhance the electrochemical CO2 reduction reaction (ECO2RR) by constructing an interface between a metal-based alloy (PdIn) nanoparticle and an oxide (In2O3), which was synthesized by a facile solution method. The oxide-derived PdIn surface has shown excellent eCO2RR activity and enhanced CO selectivity with a Faradaic efficiency (FE) of 92.13% at -0.9 V (vs RHE). On the other hand, surface PdO formation due to charge transfer on the bare PdIn alloy reduces the CO2RR activity. With the support of in situ (EXAFS and IR) and ex situ (XPS, Raman) spectroscopic techniques, the optimum presence of the Pd-In-O interface has been identified as a crucial parameter for enhancing eCO2RR toward CO in a reducing atmosphere. The influence of eCO2RR duration is reported to affect the overall performance by switching the product selectivity from H2 (from water reduction) to CO (from eCO2RR) on the oxide-derived alloy surface. This work also succeeded in the multifold enhancement of the current density by employing the gas diffusion electrode (GDE) and optimizing its process parameters in a flow cell configuration.

Structure-Tailored Surface Oxide on Cu-Ga Intermetallics Enhances CO2 Reduction Selectivity to Methanol at Ultralow Potential.

Electrochemical CO2 reduction reaction (eCO2 RR) is performed on two intermetallic compounds formed by copper and gallium metals (CuGa2 and Cu9 Ga4 ). Among them, CuGa2 selectively converts CO2 to methanol with remarkable Faradaic efficiency of 77.26% at an extremely low potential of -0.3 V vs RHE. The high performance of CuGa2 compared to Cu9 Ga4 is driven by its unique 2D structure, which retains surface and subsurface oxide species (Ga2 O3 ) even in the reduction atmosphere. The Ga2 O3 species is mapped by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) techniques and electrochemical measurements. The eCO2 RR selectivity to methanol are decreased at higher potential due to the lattice expansion caused by the reduction of the Ga2 O3 , which is probed by in situ XAFS, quasi in situ powder X-ray diffraction, and ex situ XPS measurements. The mechanism of the formation of methanol is visualized by in situ infrared (IR) spectroscopy and the source of the carbon of methanol at the molecular level is confirmed from the isotope-labeling experiments in presence of 13 CO2 . Finally, to minimize the mass transport limitations and improve the overall eCO2 RR performance, a poly(tetrafluoroethylene)-based gas diffusion electrode is used in the flow cell configuration.

Diversity in Crystal Structure and Physical Properties of RETX3 (RE - Rare Earth, T - Transition Metal, X - Main Group Element) Intermetallics.

Rare Earth (re) based intermetallics are a fascinating class of inorganic compounds due to the presence of highly localized f-electrons. Among the ternary intermetallics, RETX3 (RE - Rare Earth, T - Transition metals, X - 13-15th elements of the main groups) is one of the most widely studied RE-based intermetallic families in terms of diverse crystal structures as well as physical properties. This perspective presents a brief account of different structural variations observed in this family of compounds. We have also discussed structure-property correlations in selected compounds in this series that show interesting physical properties such as spin-glass behavior, superconductivity, heavy fermion behavior, Kondo behavior, etc. The origin of different physical properties of these compounds is also discussed in brief by correlating their crystal structures.

Structure-Tailored Non-Noble Metal-based Ternary Chalcogenide Nanocrystals for Pt-like Electrocatalytic Hydrogen Production.

A facile microwave-assisted strategy was employed to synthesize Ni3 Bi2 S2 nanocrystals. Variation in the synthesis conditions tuned the composition of monoclinic and orthorhombic phases of Ni3 Bi2 S2 . The electrochemical hydrogen evolution activity of the catalyst with highest percentage of monoclinic phase demonstrated a negligible onset potential of only 24 mV close to that of state-of-the-art Pt/C with an overpotential as low as 88 mV. Density functional theory calculations predicted the monoclinic phase exhibit the lowest adsorption free energy corresponding to hydrogen adsorption ( Δ G ads H * ) and, therefore, the highest hydrogen evolution activity amongst the considered phases. The quasi-2D structure of monoclinic phase facilitated an increased charge-transfer between Ni and Bi, favoring the downward shift of the d-band center to enhance the catalytic activity.

An Overview on Pt3 X Electrocatalysts for Oxygen Reduction Reaction.

The activity of Pt towards oxygen reduction reaction (ORR) can be enhanced by alloying it with secondary metals. They can be grouped into three different classes: alloys, bimetallics and intermetallics. Although alloys and bimetallics exhibit enhanced performance, often they are limited by metal dissolution and resulted in poor durability. This invokes the need on the development of ordered intermetallics. In this minireview we comprehensively present the recent progress and developments of Pt3 X alloys and intermetallics towards ORR. Additionally, major technical challenges and possible future research directions to overcome these challenges are discussed to facilitate further research in this area.

Correction: Conductive interface promoted bifunctional oxygen reduction/evolution activity in an ultra-low precious metal based hybrid catalyst.

Correction for 'Conductive interface promoted bifunctional oxygen reduction/evolution activity in an ultra-low precious metal based hybrid catalyst' by Shreya Sarkar et al., Chem. Commun., 2021, 57, 1951-1954, DOI: 10.1039/D0CC08225B.

Conductive interface promoted bifunctional oxygen reduction/evolution activity in an ultra-low precious metal based hybrid catalyst.

Ultra low PtPd alloy deposited on Ni12P5 nanostructures (PtPd/Ni12P5) exhibited enhanced ORR activity (onset: 1.003 V and E1/2:0.95 V) on par with commercial Pt/C and superior OER activity with 81% reduction of the precious metal compared to the commercial catalyst.

Highly efficient bifunctional oxygen reduction/evolution activity of a non-precious nanocomposite derived from a tetrazine-COF.

We report a novel s-tetrazine based covalent organic framework (TZA-COF) and its hybrid nanocomposites with reduced graphene oxide (TZA-COF-rGO) and Co metal to illustrate novel structure-activity relationships in this class of compounds for electrocatalytic oxygen reduction reaction (ORR). The Co-impregnated hybrid composites (TZA-COF-rGO-Co) were further annealed to yield Co-encapsulated nitrogen doped graphitic carbon (Co@NC-600), which exhibited excellent ORR activity comparable to that of the state-of-the art Pt/C in terms of onset potential, E1/2 (half-wave potential), 4e- reduction selectivity and methanol tolerance. Sequential mechanistic analyses of activity enhancement and electron transfer pathways for the ORR, at different stages of controlled catalyst engineering, elucidated the crucial role of active sites and overall catalyst nature in tuning the ORR mechanism. Co@NC-600 also exhibited high oxygen evolution reaction (OER) activity under alkaline conditions which makes it one of the most efficient non-precious metal bifunctional catalysts, capable of catalyzing complex 4e- reduction processes like the ORR and OER.