Heterogeneous Catalysis in Production and Utilization of Formic Acid for Renewable Energy.

As the cleanest energy source, hydrogen has been followed with interest by researchers around the world. However, due to the internal low density of hydrogen, it cannot be stored and used efficiently which limits the hydrogen application on a huge scale. Chemical hydrogen storage is considered as a useful method for efficient handling and storage. Due to its excellent safety, formic acid stands out. It is worth noting that the matter and energy conversion is established based on formic acid, which is not referred to in the previous documentation. In this review, the latest development of research on heterogeneous catalysis via production and application of formic acid for energy application is reported. The matter and energy conversion based on formic acid are both discussed systematically. More importantly, with formic acid as the node, biomass energy shows potential to be in a dominant position in the energy conversion process. In addition, the catalytic mechanism is also mentioned. This review can provide the current state in this field and the new inspirations for developing superior catalytic systems.

Surface Modulation of 3D Porous CoNiP Nanoarrays In Situ Grown on Nickel Foams for Robust Overall Water Splitting.

The careful design of nanostructures and multi-compositions of non-noble metal-based electrocatalysts for highly efficient electrocatalytic hydrogen and oxygen evolution reaction (HER and OER) is of great significance to realize sustainable hydrogen release. Herein, bifunctional electrocatalysts of the three-dimensional (3D) cobalt-nickel phosphide nanoarray in situ grown on nickel foams (CoNiP NA/NF) were synthesized through a facile hydrothermal method followed by phosphorization. Due to the unique self-template nanoarray structure and tunable multicomponent system, the CoNiP NA/NF samples present exceptional activity and durability for HER and OER. The optimized sample of CoNiP NA/NF-2 afforded a current density of 10 mA cm-2 at a low overpotential of 162 mV for HER and 499 mV for OER, corresponding with low Tafel slopes of 114.3 and 79.5 mV dec-1, respectively. Density functional theory (DFT) calculations demonstrate that modulation active sites with appropriate electronic properties facilitate the interaction between the catalyst surface and intermediates, especially for the adsorption of absorbed H* and *OOH intermediates, resulting in an optimized energy barrier for HER and OER. The 3D nanoarray structure, with a large specific surface area and abundant ion channels, can enrich the electroactive sites and enhance mass transmission. This work provides novel strategies and insights for the design of robust non-precious metal catalysts.

Engineering Interface on a 3D CoxNi1-x(OH)2@MoS2 Hollow Heterostructure for Robust Electrocatalytic Hydrogen Evolution.

Clarifying the responsibilities and constructing the synergy of different active phases are of great significance but still an urgent challenge for the heterostructure catalyst to improve the hydrogen evolution reaction (HER) process. Here, three-dimensional (3D) CoxNi(1-x)(OH)2 hollow structure integrating MoS2 nanosheet catalysts [CoxNi(1-x)(OH)2@MoS2] were ingeniously designed and prepared. This unique structure has realized the construction of a dual active phase for the optimized stepwise-synergetic hydrogen evolution process over a universal pH range through interface assembly engineering. Meanwhile, the 3D hollow heterostructure with a high surface-to-volume ratio can effectively avoid the agglomeration of MoS2 and enhance the CoxNi(1-x)(OH)2-MoS2 heterointerfaces. Thus, superior HER activity and stability were obtained over the universal pH range. Density functional theory calculation reveals that CoxNi(1-x)(OH)2 and MoS2 phases provide efficient active sites for rate-determining water dissociation and H* adsorption/H2 generation on CoxNi(1-x)(OH)2-MoS2 heterointerfaces, respectively, resulting in an optimized energy barrier for HER. This work proposes a constructive strategy to design highly efficient electrocatalysts based on the heterointerface with a defined responsible active phase of electrocatalysts.

Advances and Prospects in Metal-Organic Frameworks as Key Nexus for Chemocatalytic Hydrogen Production.

Hydrogen is a clean and sustainable energy carrier, which is considered a promising alternative for fossil fuels to solve the global energy crisis and respond to climate change. Social concerns on its safe storage promote continuous exploration of alternatives to traditional storage methods. In this case, chemical hydrogen storage materials initiate plentiful research with special attention to the design of heterogeneous catalysts that can enhance efficient and highly selective hydrogen production. Metal-organic frameworks (MOFs), a kind of unique crystalline porous materials featuring highly ordered porosities and tailorable structures, can provide various active sites (i.e., metal nodes, functional linkers, and defects) for heterogeneous catalysis. Furthermore, the easy construction of active sites in highly ordered MOFs, which can work as plate for the delicate active site engineering, make them ideal candidates for a variety of heterogeneous catalysts including chemocatalytic hydrogen production. This review concentrates on the application of MOFs as heterogeneous catalysts or catalyst supports in chemocatalytic hydrogen production. Recent progresses of MOFs as catalysts for chemocatalytic hydrogen production are comprehensively summarized. The research methods, mechanism analyses, and prospects of MOFs in this field are discussed. The challenges in future industrial applications of MOFs as catalysts for hydrogen production are proposed.

Effect of ZnSO4, MnSO4 and FeSO4 on the Partial Hydrogenation of Benzene over Nano Ru-Based Catalysts.

Nano Ru-based catalysts, including monometallic Ru and Ru-Zn nanoparticles, were synthesized via a precipitation method. The prepared catalysts were evaluated on partial hydrogenation of benzene towards cyclohexene generation, during which the effect of reaction modifiers, i.e., ZnSO4, MnSO4, and FeSO4, was investigated. The fresh and the spent catalysts were thoroughly characterized by XRD, TEM, SEM, XPS, XRF, and DFT studies. It was found that Zn2+ or Fe2+ could be adsorbed on the surface of a monometallic Ru catalyst, where a stabilized complex could be formed between the cations and the cyclohexene. This led to an enhancement of catalytic selectivity towards cyclohexene. Furthermore, electron transfer was observed from Zn2+ or Fe2+ to Ru, hindering the catalytic activity towards benzene hydrogenation. In comparison, very few Mn2+ cations were adsorbed on the Ru surface, for which no cyclohexene could be detected. On the other hand, for Ru-Zn catalyst, Zn existed as rodlike ZnO. The added ZnSO4 and FeSO4 could react with ZnO to generate (Zn(OH)2)5(ZnSO4)(H2O) and basic Fe sulfate, respectively. This further benefited the adsorption of Zn2+ or Fe2+, leading to the decrease of catalytic activity towards benzene conversion and the increase of selectivity towards cyclohexene synthesis. When 0.57 mol·L-1 of ZnSO4 was applied, the highest cyclohexene yield of 62.6% was achieved. When MnSO4 was used as a reaction modifier, H2SO4 could be generated in the slurry via its hydrolysis, which reacted with ZnO to form ZnSO4. The selectivity towards cyclohexene formation was then improved by the adsorbed Zn2+.

Phosphorus-Doped 3D RuCo Nanowire Arrays on Nickel Foam with Enhanced Electrocatalytic Activity for Overall Water Splitting.

It is especially significant to design and construct high-performance and stable three-dimensional (3D) bifunctional nanoarchitecture electrocatalysts toward overall water splitting. Herein, we have constructed 3D self-supported phosphorus-doped ruthenium-cobalt nanowires on nickel foams (RuCoP/NF) via a simple hydrothermal reaction followed by a low-temperature phosphating reaction. Doping P can not merely enhance the intrinsic activity of electrocatalysts for overall water splitting but at the same time increase electrochemical surface areas (ECSAs) to expose more accessible active sites. As a 3D bifunctional catalyst, RuCoP/NF demonstrates superior performance for HER (44 mV@10 mA cm-2) and OER (379 mV@50 mA cm-2) in 1.0 M KOH electrolyte solution. The overall water-splitting system was assembled using RuCoP/NF as both anode and cathode. Besides, it exhibits a voltage of 1.533 V at a current density of 10 mA cm-2 and long-term durability within 24 h. P-dopant changes the electron structure of Ru and Co, which is conducive to the formation of Ruδ- and Coδ+, resulting in the adjustment of binding H*/OH* and the improvement of the overall water-splitting reaction kinetics. This work provides a facile method to produce heteroatom-doped and high-performance catalysts for efficient overall water splitting.

Investigation on Mn3O4 Coated Ru Nanoparticles for Partial Hydrogenation of Benzene towards Cyclohexene Production Using ZnSO4, MnSO4 and FeSO4 as Reaction Additives.

Mn3O4 coated Ru nanoparticles (Ru@Mn3O4) were synthesized via a precipitation-reduction-gel method. The prepared catalysts were evaluated for partial hydrogenation of benzene towards cyclohexene generation by applying ZnSO4, MnSO4 and FeSO4 as reaction additives. The fresh and spent catalysts were thoroughly characterized by XRD, X ray fluorescence (XRF), XPS, TEM and N2-physicalsorption in order to understand the promotion effect of Mn3O4 as the modifier as well as ZnSO4, MnSO4 and FeSO4 as reaction additives. It was found that 72.0% of benzene conversion and 79.2% of cyclohexene selectivity was achieved after 25 min of reaction time over Ru@Mn3O4 with a molar ratio of Mn/Ru being 0.46. This can be rationalized in terms of the formed (Zn(OH)2)3(ZnSO4)(H2O)3 on the Ru surface from the reaction between Mn3O4 and the added ZnSO4. Furthermore, Fe2+ and Fe3+ compounds could be generated and adsorbed on the surface of Ru@Mn3O4 when FeSO4 is applied as a reaction additive. The most electrons were transferred from Ru to Fe, resulting in that lowest benzene conversion of 1.5% and the highest cyclohexene selectivity of 92.2% after 25 min of catalytic experiment. On the other hand, by utilizing MnSO4 as an additive, no electrons transfer was observed between Ru and Mn, which lead to the complete hydrogenation of benzene towards cyclohexane within 5 min. In comparison, moderate amount of electrons were transferred from Ru to Zn2+ in (Zn(OH)2)3(ZnSO4)(H2O)3 when ZnSO4 is used as a reaction additive, and the highest cyclohexene yield of 57.0% was obtained within 25 min of reaction time.

Cobalt Phosphide-Embedded Reduced Graphene Oxide as a Bifunctional Catalyst for Overall Water Splitting.

It is highly desirable to design high-efficiency stable and low-price catalysts in the electrocatalysis field. Herein, we reported a cobalt phosphide (Co2P)-loaded reduced graphene oxide (rGO) composite catalyst (rGO/Co2P) prepared via the convenient hydrothermal and H2 reduction methods. The rGO/Co2P catalyst reduced at 800 °C (rGO/Co2P-800) shows superior electrocatalytic activities for hydrogen evolution reaction and oxygen evolution reaction in 1.0 M KOH solution, achieving an overpotential of 134 and 378 mV, respectively, at a current density of 10 mA cm-2. Moreover, the catalyst can not only maintain stability for a long time in alkaline solution but also in acid media because of the protection of the rGO layers. The superior performance of this catalyst is attributed to the synergy between the carbon layer and transition-metal phosphides. The Co2P nanoparticles have a high degree of dispersion, which prevents agglomeration, thereby exposing more active sites. Moreover, rGO protects the exposed metal particles while providing more electroconductivity to the material. This work provides an efficient route for the development of bifunctional electrocatalysts with excellent performance and stability, which provides new ideas toward overall water splitting.

Surface Engineering on Nickel-Ruthenium Nanoalloys Attached Defective Carbon Sites as Superior Bifunctional Electrocatalysts for Overall Water Splitting.

Herein, we report a novel catalyst of nickel-ruthenium alloy nanoparticles (NPs) homogeneously enriched in the wall of multiwalled carbon nanotubes (denoted as NiRu@MWCNTs) via a facile plasma reduction method. The NiRu@MWCNTs exhibits remarkable electrocatalytic activity and stability for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The required overpotentials to drive a current density of 10 mA cm-2 (η10) over NiRu@MWCNTs are only 14 and 240 mV, corresponding to Tafel slopes of 32 and 55 mV dec-1 for the HER and OER in alkaline medium, respectively. Furthermore, the NiRu@MWCNTs electrolyzer shows low η10 of 330, 380, and 280 mV in acidic, neutral, and alkaline media, respectively. Density functional theory (DFT) calculations and experimental results reveal that the NiRu alloy NPs attached to the defective and nondefective carbon are the key active sites for the HER and OER, respectively, thus resulting in superior isolated synergistic bifunctional active sites for overall water splitting. Our work provides a promising strategy for efficient synthesis of robust catalysts with specific bifunctional active sites for overall water splitting in a wide pH range, along with deep insight into the catalytic mechanism.

3D free-standing nitrogen-doped reduced graphene oxide aerogel as anode material for sodium ion batteries with enhanced sodium storage.

Sodium ion batteries have drawn extensive attentions for large-scale energy storage to replace lithium ion batteries primarily due to the natural abundance of sodium resource and low cost, but their energy density and electrochemical performance are hindered by the sluggish diffusion kinetics of sodium ion. Herein, free-standing nitrogen-doped graphene aerogel has been fabricated via hydrothermal reaction as the potential anode material for sodium ion batteries. The three dimensional porous network structure of the graphene aerogel provides sufficient interstitial space for sodium ion accommodation, allowing fast and reversible ion intercalation/de-intercalation. The nitrogen doping could introduce defects on the graphene sheets, making the feasible transport of large-sized sodium ion. Benefiting from the effective structure and nitrogen doping, the obtained material demonstrates high reversible capacities, good cycling performance (287.9 mA h g-1 after 200 cycles at a current density of 100 mA g-1), especially superior rate capability (151.9 mA h g-1 at a high current density of 5 A g-1).

Heterophase-structured nanocrystals as superior supports for Ru-based catalysts in selective hydrogenation of benzene.

ZrO2 heterophase structure nanocrystals (HSNCs) were synthesized with tunable ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2). The phase mole ratio of m-ZrO2 versus t-ZrO2 in ZrO2 HSNCs was tuned from 40% to 100%. The concentration of the surface hydroxyl groups on m-ZrO2 is higher than that on t-ZrO2. ZrO2 HSNCs have different surface hydroxyl groups on two crystalline phases. This creates more intimate synergistic effects than their single-phase counterparts. The ZrO2 HSNCs were used as effective supports to fabricate heterophase-structured Ru/ZrO2 catalysts for benzene-selective hydrogenation. The excellent catalytic performance including high activity and selectivity is attributed to the heterogeneous strong/weak hydrophilic interface and water layer formed at the m-ZrO2/t-ZrO2 catalyst junction.

Design and Tailoring of the 3D Macroporous Hydrous RuO2 Hierarchical Architectures with a Hard-Template Method for High-Performance Supercapacitors.

In this work, RuO2 honeycomb networks (RHCs) and hollow spherical structures (RHSs) were rationally designed and synthesized with modified-SiO2 as a sacrificial template via two hydrothermal approaches. At a high current density of 20 A g-1, the two hierarchical porous RuO2·xH2O frameworks showed the specific capacitance as high as 628 and 597 F g-1; this is about 80% and 75% of the capacitance retention of 0.5 A g-1 for RHCs and RHSs, respectively. Even after 4000 cycles at 5 A g-1, the RHCs and RHSs can still remain at 86% and 91% of their initial specific capacitances, respectively. These two hierarchical frameworks have a well-defined pathway that benefits for the transmission/diffusion of electrolyte and surface redox reactions. As a result, they exhibit good supercapacitor performance in both acid (H2SO4) and alkaline (KOH) electrolytes. As compared to RuO2 bulk structure and similar RuO2 counterpart reported in pseudocapacitors, the two hierarchical porous RuO2·xH2O frameworks have better energy storage capabilities, high-rate performance, and excellent cycling stability.