Unconventional hcp/fcc Nickel Heteronanocrystal with Asymmetric Convex Sites Boosts Hydrogen Oxidation.

Developing non-platinum group metal catalysts for the sluggish hydrogen oxidation reaction (HOR) is critical for alkaline fuel cells. To date, Ni-based materials are the most promising candidates but still suffer from insufficient performance. Herein, we report an unconventional hcp/fcc Ni (u-hcp/fcc Ni) heteronanocrystal with multiple epitaxial hcp/fcc heterointerfaces and coherent twin boundaries, generating rugged surfaces with plenty of asymmetric convex sites. Systematic analyses discover that such convex sites enable the adsorption of *H in unusual bridge positions with weakened binding energy, circumventing the over-strong *H adsorption on traditional hollow positions, and simultaneously stabilizing interfacial *H2O. It thus synergistically optimizes the HOR thermodynamic process as well as reduces the kinetic barrier of the rate-determining Volmer step. Consequently, the developed u-hcp/fcc Ni exhibits the top-rank alkaline HOR activity with a mass activity of 40.6 mA mgNi-1 (6.3 times higher than fcc Ni control) together with superior stability and high CO-tolerance. These results provide a paradigm for designing high-performance catalysts by shifting the adsorption state of intermediates through configuring surface sites.

CO-Tolerant Hydrogen Oxidation Electrocatalysts for Low-Temperature Hydrogen Fuel Cells.

The severe performance degradation of low-temperature hydrogen fuel cells upon exposure to trace amounts of carbon monoxide (CO) impurities in reformate hydrogen fuels is one of the challenges that hinders their commercialization. Despite significant efforts that have been made, the CO-tolerance performance of electrocatalysts for the hydrogen oxidation reaction (HOR) is still unsatisfactory. This Perspective discusses the path forward for the rational design of CO-tolerant HOR electrocatalysts. The fundamentals of the CO-tolerant mechanisms on commercialized platinum group metal (PGM) electrocatalysts via either promoting CO electrooxidation or weakening CO adsorption are provided, and comprehensive discussions based on these strategies are presented with typical examples. Given the recent progress, some emerging strategies, including blocking CO diffusion with a barrier layer and developing non-PGM HOR catalysts, are also discussed. We conclude with a discussion of the strengths and limitations of these strategies along with the perspectives of the major challenges and opportunities for future research on CO-tolerant HOR electrocatalysts.

Colloidal Zeta Potential Modulation as a Handle to Control the Crystallization Kinetics of Tin Halide Perovskites for Photovoltaic Applications.

Tin halide perovskites (THPs) have demonstrated exceptional potential for various applications owing to their low toxicity and excellent optoelectronic properties. However, the crystallization kinetics of THPs are less controllable than its lead counterpart because of the higher Lewis acidity of Sn2+, leading to THP films with poor morphology and rampant defects. Here, a colloidal zeta potential modulation approach is developed to improve the crystallization kinetics of THP films inspired by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. After adding 3-aminopyrrolidine dihydro iodate (APDI2) in the precursor solution to change the zeta potential of the pristine colloids, the total interaction potential energy between colloidal particles with APDI2 could be controllably reduced, resulting in a higher coagulation probability and a lower critical nuclei concentration. In situ laser light scattering measurements confirmed the increased nucleation rate of the THP colloids with APDI2. The resulting film with APDI2 shows a pinhole-free morphology with fewer defects, achieving an impressive efficiency of 15.13 %.

Structure of Amorphous Selenium: Small Ring, Big Controversy.

Selenium (Se) discovered in 1817 belongs to the family of chalcogens. Surprisingly, despite the long history of over two centuries and the chemical simplicity of Se, the structure of amorphous Se (a-Se) remains controversial to date regarding the dominance of chains versus rings. Here, we find that vapor-deposited a-Se is composed of disordered rings rather than chains in melt-quenched a-Se. We further reveal that the main origin of this controversy is the facile transition of rings to chains arising from the inherent instability of rings. This transition can be inadvertently triggered by certain characterization techniques themselves containing above-bandgap illumination (above 2.1 eV) or heating (above 50 °C). We finally build a roadmap for obtaining accurate Raman spectra by using above-bandgap excitation lasers with low photon flux (below 1017 phs m-2 s-1) and below-bandgap excitation lasers measured at low temperatures (below -40 °C) to minimize the photoexcitation- and heat-induced ring-to-chain transitions.

Facile Hydrogen-Bonding Assisted Crystallization Modulation for Large-area High-quality CsPbI2 Br Films and Efficient Solar Cells.

The thermally stable inorganic cesium-based perovskites promise efficient and stable photovoltaics. Unfortunately, the strong ionic bonds lead to uncontrollable rapid crystallization, making it difficult in fabricating large-area black-phase film for photovoltaics. Herein, we developed a facile hydrogen-bonding assisted strategy for modulating the crystallization of CsPbI2 Br to achieve uniform large-area phase-pure films with much-reduced defects. The simple addition of methylamine acetate in precursors not only promotes the formation of intermediate phase via hydrogen bonding to circumvent the direct crystallization of CsPbI2 Br from ionic precursors but also widens the film processing window, thus enabling to fabricate large-area high-quality phase-pure CsPbI2 Br film under benign conditions. Combining with stable dopant-free poly(3-hexylthiophene), the CsPbI2 Br solar cells achieve the record-high efficiencies of 18.14 % and 16.46 % for 0.1 cm2 and 1 cm2 active area, respectively. The obtained high efficiency of 38.24 % under 1000 lux illumination suggests its potential in indoor photovoltaics for powering the Internet of Things, etc.

High-Density CuInS2 Quantum Dots for Efficient and Stable CO2 Electroreduction.

Electrochemically converting CO2 back into fuels and chemicals is promising in alleviating the greenhouse effect worldwide. Various high-efficiency catalysts have been achieved, yet the unsatisfied structural stability under CO2 electrolysis conditions restricts their practical application. Herein, a sub-5 nm sized CuInS2 quantum dots (CIS-QDs) based electrocatalyst for converting CO2 into CO are developed. Taking advantage of the stable M─Ch (metal-chalcogenide) covalent bonds, and unique p-block metal properties, the as-prepared catalyst exhibits excellent structural stability under large overpotentials and can achieve a high CO Faradaic efficiency (FE) of 86% (total CO2 reduction FE of 89%) at -0.65 V versus reversible hydrogen electrode with long-term durability of 40 h and outstanding current densities of 10.6 mA cm-2 simultaneously. Furthermore, detailed electrochemical analyses revealed that the excellent performance of the as-prepared catalysts shall be attributed to the high-density active sites and fast charge transfer brought by the ultrasmall size of CIS-QDs. This work provides insights into the design of high-density and stable catalytic sites for developing high-performance electrocatalysts.

Dual Ni/Co-hemin metal-organic framework-PrGO for high-performance asymmetric hybrid supercapacitor.

In this study, we conducted direct synthesis of a dual metal-organic framework (Ni/Co-Hemin MOF) on phosphorous-doped reduced graphene oxide (PrGO) to serve as an active material in high-performance asymmetrical supercapacitors. The nanocomposite was utilized as an active material in supercapacitors, exhibiting a noteworthy specific capacitance of 963 C g-1 at 1.0 A g-1, along with a high rate capability of 68.3% upon increasing the current density by 20 times, and superior cycling stability. Our comprehensive characterization and control experiments indicated that the improved performance can be attributed to the combined effect of the dual MOF and the presence of phosphorous, influencing the battery-type supercapacitor behavior of GO. Additionally, we fabricated an asymmetric hybrid supercapacitor (AHSC) using Ni/Co-Hemin/PrGO/Nickel foam (NF) and activated carbon (AC)/NF. This AHSC demonstrated a specific capacitance of 281 C g-1 at 1.0 A g-1, an operating voltage of 1.80 V, an impressive energy density of 70.3 Wh kg-1 at a high power density of 0.9 kW kg-1. Notably, three AHSC devices connected in series successfully powered a clock for approximately 42 min. These findings highlight the potential application of Hemin-based MOFs in advanced supercapacitor systems.

Unconventional Bilateral Compressive Strained Ni-Ir Interface Synergistically Accelerates Alkaline Hydrogen Oxidation.

The alkaline hydrogen oxidation reaction (HOR) involves the coupling of adsorbed hydrogen (Had) and hydroxyl (OHad) species and is thus orders of magnitude slower than that in acid media. According to the Sabatier principle, developing electrocatalysts with appropriate binding energy for both intermediates is vital to accelerating the HOR though it is still challenging. Herein, we propose an unconventional bilateral compressive strained Ni-Ir interface (Ni-Ir(BCS)) as efficient synergistic HOR sites. Density functional theory (DFT) simulations reveal that the bilateral compressive strain effect leads to the appropriate adsorption for both Had and OHad, enabling their coupling thermodynamically spontaneous and kinetically preferential. Such Ni-Ir(BCS) is experimentally achieved by embedding sub-nanometer Ir clusters in graphene-loaded high-density Ni nanocrystals (Ni-Ir(BCS)/G). As predicted, it exhibits a HOR mass activity of 7.95 and 2.88 times those of commercial Ir/C and Pt/C together with much enhanced CO tolerance, respectively, ranking among the most active state-of-the-art HOR catalysts. These results provide new insights into the rational design of advanced electrocatalysts involving coordinated adsorption and activation of multiple reactants.

In-situ constructed Cu/CuNC interfaces for low-overpotential reduction of CO2 to ethanol.

Electrochemical CO2 reduction (ECR) to high-value multi-carbon (C2+) products is critical to sustainable energy conversion, yet the high energy barrier of C-C coupling causes catalysts to suffer high overpotential and low selectivity toward specific liquid C2+ products. Here, the electronically asymmetric Cu-Cu/Cu-N-C (Cu/CuNC) interface site is found, by theoretical calculations, to enhance the adsorption of *CO intermediates and decrease the reaction barrier of C-C coupling in ECR, enabling efficient C-C coupling at low overpotential. The catalyst consisting of high-density Cu/CuNC interface sites (noted as ER-Cu/CuNC) is then accordingly designed and constructed in situ on the high-loading Cu-N-C single atomic catalysts. Systematical experiments corroborate the theoretical prediction that the ER-Cu/CuNC boosts electrocatalytic CO2-to-ethanol conversion with a Faradaic efficiency toward C2+ of 60.3% (FEethanol of 55%) at a low overpotential of -0.35 V. These findings provide new insights and an attractive approach to creating electronically asymmetric dual sites for efficient conversion of CO2 to C2+ products.

Interfacial assembly of binary atomic metal-Nx sites for high-performance energy devices.

Anion-exchange membrane fuel cells and Zn-air batteries based on non-Pt group metal catalysts typically suffer from sluggish cathodic oxygen reduction. Designing advanced catalyst architectures to improve the catalyst's oxygen reduction activity and boosting the accessible site density by increasing metal loading and site utilization are potential ways to achieve high device performances. Herein, we report an interfacial assembly strategy to achieve binary single-atomic Fe/Co-Nx with high mass loadings through constructing a nanocage structure and concentrating high-density accessible binary single-atomic Fe/Co-Nx sites in a porous shell. The prepared FeCo-NCH features metal loading with a single-atomic distribution as high as 7.9 wt% and an accessible site density of around 7.6 × 1019 sites g-1, surpassing most reported M-Nx catalysts. In anion exchange membrane fuel cells and zinc-air batteries, the FeCo-NCH material delivers peak power densities of 569.0 or 414.5 mW cm-2, 3.4 or 2.8 times higher than control devices assembled with FeCo-NC. These results suggest that the present strategy for promoting catalytic site utilization offers new possibilities for exploring efficient low-cost electrocatalysts to boost the performance of various energy devices.

Regioselective Multisite Atomic-Chlorine Passivation Enables Efficient and Stable Perovskite Solar Cells.

Passivating defects using organic halide salts, especially chlorides, is an effective method to improve power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) arising from the stronger Pb-Cl bonding than Pb-I and Pb-Br bonding. However, Cl- anions with a small radius are prone to incorporation into the perovskite lattice that distorts the lead halide octahedron, degrading the photovoltaic performance. Here, we substitute atomic-Cl-containing organic molecules for widely used ionic-Cl salts, which not only retain the efficient passivation by Cl but also prevent the incorporation of Cl into the bulk lattice, benefiting from the strong covalent bonding between Cl atoms and organic frameworks. We find that only when the distance of Cl atoms in single molecules matches well with the distance of halide ions in perovskites can such a configuration maximize the defect passivation. We thereby optimize the molecular configuration to enable multiple Cl atoms in an optimal spatial position to maximize their binding with surface defects. The resulting PSCs achieve a certified PCE of 25.02%, among the highest PCEs for PSCs, and retain 90% of their initial PCE after 500 h of continuous operation.

Fully Dispersed IrOx Atomic Clusters Enable Record Photoelectrochemical Water Oxidation of Hematite in Acidic Media.

Ir-based materials are still the benchmark catalysts for various reactions in acidic environment, but the high loading and low atom utilization limit their large-scale deployment. Herein, we report an effective strategy for implanting fully dispersed iridium-oxide atomic clusters onto hematite for boosting photoelectrochemical water oxidation in acidic solution. The resulting photoanode achieves a record-high photocurrent of 1.35 mA cm-2 at 1.23 V, corresponding to a mass activity of 172.70 A g-1 (3 times higher than electrodeposited control sample) and demonstrating the merits from the high atomic utilization of Ir. The systematically experimental and theoretical results reveal that the performance improvement correlates with the modulated electronic structure including the adjusted Fermi level and d-band center, which significantly enhances charge separation efficiency and promotes the conversion from intermediate *O into *OOH.

Evolution of Stabilized 1T-MoS2 by Atomic-Interface Engineering of 2H-MoS2 /Fe-Nx towards Enhanced Sodium Ion Storage.

Metallic conductive 1T phase molybdenum sulfide (MoS2 ) has been identified as promising anode for sodium ion (Na+ ) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic-interface engineering is employed for constructing 2H-MoS2 layers assembled on single atomically dispersed Fe-N-C (SA Fe-N-C) anode material that boosts its reversible capacity. The work-function-driven-electron transfer occurs from SA Fe-N-C to 2H-MoS2 via the Fe-S bonds, which enhances the adsorption of Na+ by 2H-MoS2 , and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS2 with the ferromagnetic spin-polarization of SA Fe-N-C occurs during the sodiation/desodiation process, which significantly enhances the Na+ storage kinetics, and thus the 1T/2H MoS2 /SA Fe-N-C display a high electronic conductivity and a fast Na+ diffusion rate.

Indoor photovoltaics awaken the world's first solar cells.

Selenium (Se) solar cells were the world's first solid-state photovoltaics reported in 1883, opening the modern photovoltaics. However, its wide bandgap (~1.9 eV) limits sunlight harvesting. Here, we revisit the world's oldest but long-ignored photovoltaic material with the emergence of indoor photovoltaics (IPVs); the absorption spectrum of Se perfectly matches the emission spectra of commonly used indoor light sources in the 400 to 700 nm range. We find that the widely used Te adhesion layer also passivates defects at the nonbonded Se/TiO2 interface. By optimizing the Te coverage from 6.9 to 70.4%, the resulting Se cells exhibit an efficiency of 15.1% under 1000 lux indoor illumination and show no efficiency loss after 1000 hours of continuous indoor illumination without encapsulation, outperforming the present IPV industry standard of amorphous silicon cells in both efficiency and stability. We further fabricate Se modules (6.75 cm2) that produce 232.6 µW output power under indoor illumination, powering a radio-frequency identification-based localization tag.

Buffering the local pH via single-atomic Mn-N auxiliary sites to boost CO2 electroreduction.

Electrocatalytic CO2 reduction driven by renewable energy has become a promising approach to rebalance the carbon cycle. Atomically dispersed transition metals anchored on N-doped carbon supports (M-N-C) have been considered as the most attractive catalysts to catalyze CO2 to CO. However, the sluggish kinetics of M-N-C limits the large-scale application of this type of catalyst. Here, it is found that the introduction of single atomic Mn-N auxiliary sites could effectively buffer the locally generated OH- on the catalytic interface of the single-atomic Ni-N-C sites, thus accelerating proton-coupled electron transfer (PCET) steps to enhance the CO2 electroreduction to CO. The constructed diatomic Ni/Mn-N-C catalysts show a CO faradaic efficiency of 96.6% and partial CO current density of 13.3 mA cm-2 at -0.76 V vs. RHE, outperforming that of monometallic single-atomic Ni-N-C or Mn-N-C counterparts. The results suggest that constructing synergistic catalytic sites to regulate the surface local microenvironment might be an attractive strategy for boosting CO2 electroreduction to value-added products.

Probing the Synergistic Effects of Mg2+ on CO2 Reduction Reaction on CoPc by In Situ Electrochemical Scanning Tunneling Microscopy.

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg2+ in CO2 reduction reaction (CO2RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO2 environment, high-contrast species are observed in the adlayer and assigned to the CO2 adsorption on CoPc. Furthermore, the contrast of the CO2-bound complex is higher in Mg2+-containing electrolytes than in Mg2+-free electrolytes, indicating the formation of the CoPc-CO2-Mg2+ complex. The surface coverage of adsorbed CO2 is positively correlated with the Mg2+ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg2+) > 30 mM. The potential step experiment indicates the higher CO2 adsorption dynamics in Mg2+-containing electrolytes than without Mg2+. The rate constants of CO2 adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.

Recent advances in metal catalyst- and oxidant-free electrochemical C-H bond functionalization of nitrogen-containing heterocycles.

The C-H functionalization of nitrogen-containing heterocycles has emerged as a powerful strategy for the construction of carbon-carbon (C-C) and carbon-heteroatom (C-X) bonds. In order to achieve efficient and selective C-H functionalization, electrochemical synthesis has attracted increasing attention. Because electrochemical anodic oxidation is ideal for replacing chemical reagents in C-H functionalization reactions. This mini-review summarizes the current knowledge and recent advances since 2017 in the synthetic utility of electrochemical transformations for the C-H functionalization of nitrogen-containing heterocycles.

Carrier Management via Integrating InP Quantum Dots into Electron Transport Layer for Efficient Perovskite Solar Cells.

Metal oxides are the most efficient electron transport layers (ETLs) in perovskite solar cells (PSCs). However, issues related to the bulk (i.e., insufficient electron mobility, unfavorable energy level position) and interface of metal oxide/perovskite (detrimental surface hydroxyl groups) limit the transport kinetics of photoinduced electrons and prevent PSCs from unleashing their theoretical efficiency potential. Herein, the inorganic InP colloid quantum dots (CQDs) with outstanding electron mobility (4600 cm2 V-1 s-1) and carboxyl (-COOH) terminal ligands were uniformly distributed into the metal oxide ETL to form consecutive electron transport channels. The hybrid InP CQD-based ETL demonstrates a more N-type characteristic with more than 3-fold improvement in electron mobility. The formation of the Sn-O-In bond facilitates electron extraction due to suitable energy level alignment between the ETL and perovskite. The strong interaction between uncoordinated Pb2+ at the perovskite/ETL interface and the -COO- in the ligand of InP CQDs reduces the density of defects in perovskite. As a result, the hybrid InP CQD-based ETL with an optimized InP ratio (18 wt %) boosts the power conversion efficiency of PSCs from 22.38 to 24.09% (certified efficiency of 23.43%). Meanwhile, the device demonstrates significantly improved photostability and atmospheric storage stability.

Solution-processed Ge(ii)-based chalcogenide thin films with tunable bandgaps for photovoltaics.

Solution processes have been widely used to construct chalcogenide-based thin-film optoelectronic and electronic devices that combine high performance with low-cost manufacturing. However, Ge(ii)-based chalcogenide thin films possessing great potential for optoelectronic devices have not been reported using solution-based processes; this is mainly attributed to the easy oxidation of intermediate Ge(ii) to Ge(iv) in the precursor solution. Here we report solution-processed deposition of Ge(ii)-based chalcogenide thin films in the case of GeSe and GeS films by introducing hypophosphorous acid as a suitable reducing agent and strong acid. This enables the generation of Ge(ii) from low-cost and stable GeO2 powders while suppressing the oxidation of Ge(ii) to Ge(iv) in the precursor solution. We further show that such solution processes can also be used to deposit GeSe1-x S x alloy films with continuously tunable bandgaps ranging from 1.71 eV (GeS) to 1.14 eV (GeSe) by adjusting the atomic ratio of S- to Se-precursors in solution, thus allowing the realization of optimal-bandgap single-junction photovoltaic devices and multi-junction devices.

Electrocatalytic Hydrogen Oxidation in Alkaline Media: From Mechanistic Insights to Catalyst Design.

With the potential to circumvent the need for scarce and cost-prohibitive platinum-based catalysts in proton-exchange membrane fuel cells, anion-exchange membrane fuel cells (AEMFCs) are emerging as alternative technologies with zero carbon emission. Numerous noble metal-free catalysts have been developed with excellent catalytic performance for cathodic oxygen reduction reaction in AEMFCs. However, the anodic catalysts for hydrogen oxidation reaction (HOR) still rely on noble metal materials. Since the kinetics of HOR in alkaline media is 2-3 orders of magnitude lower than that in acidic media, it is a major challenge to either improve the performance of noble metal catalysts or to develop high-performance noble metal-free catalysts. Additionally, the mechanisms of alkaline HOR are not yet clear and still under debate, further hampering the design of electrocatalysts. Against this backdrop, this review starts with the prevailing theories for alkaline HOR on the basis of diverse activity descriptors, i.e., hydrogen binding energy theory and bifunctional theory. The design principles and recent advances of HOR catalysts employing the aforementioned theories are then summarized. Next, the strategies and recent progress in improving the antioxidation capability of HOR catalysts, a thorny issue which has not received sufficient attention, are discussed. Moreover, the significance of correlating computational models with real catalyst structure and the electrode/electrolyte interface is further emphasized. Lastly, the remaining controversies about the alkaline HOR mechanisms as well as the challenges and possible research directions in this field are presented.