CO2‐Mediated H2 Storage‐Release with Nanostructured Catalysts: Recent Progresses,Challenges, and Perspectives

It has increasingly become clear that economic growth worldwide based on fossil fuel energy supply cannot be sustained; thus, alternative, renewable energy sources and carriers must be urgently developed to maintain growth. Dihydrogen (H₂), which can produce energy without generating environmental pollutants, can play a major role in this endeavor. However, to use H₂ in renewable energy systems, systems and materials that can store and transport it, or convert it into easier‐to‐handle/transport synthetic fuels, need to be developed. In this article, first, many of the issues related to both homogeneous and heterogeneous catalysts that are being developed to help H₂'s use as energy carrier are discussed. More focus is then given to heterogeneous nanocatalysts that are developed for reversible CO₂‐mediated hydrogenation and dehydrogenation reactions involving chemical hydrogen carriers and delivery systems, mainly formic acid/CO₂ and formate/bicarbonate. The challenges associated with the development of nanocatalysts based on earth‐abundant elements for dehydrogenation and hydrogenation reactions of these compounds for H₂ storage and release are emphasized in the discussions. Finally, the pressing research questions and major issues that need to be addressed in the near future to help the realization of the “hydrogen economy” are outlined.     

Complete Dehydrogenation of N2H4BH3 over Noble‐Metal‐Free Ni0.5Fe0.5–CeOx/MIL‐101 with High Activity and 100% H2 Selectivity

Efficient and selective dehydrogenation of hydrazine borane (HB), a novel hydrogen storage material with very high hydrogen content (HB, 15.4 wt%), is a key challenge for a fuel‐cell‐based hydrogen economy. However, even using the noble metal catalysts for HB decomposition, the activities are still far from satisfying, to say nothing of non‐noble‐metal‐containing catalysts. In response, as a proof‐of‐concept experiment, herein, noble‐metal‐free NiFe–CeO_x nanoparticles are successfully immobilized on an MIL‐101 support without surfactant by a simple liquid impregnation method. Unexpectedly, the resultant Ni_0.5Fe_0.5–CeO_x/MIL‐101 catalyst shows good performance, including 100% H₂ selectivity, 100% conversion, and record catalytic activity (351.3 h^?1) for hydrogen generation at mild temperature, which is even better than most of the noble metal heterogeneous catalysts and might be attributed to the good dispersion and uniform particle size of the Ni_0.5Fe_0.5–CeO_x nanoparticles due to steric restrictions effect of the MIL‐101 support. Additionally, extending MIL‐101 to some other important kinds of metal–organic framework (MOF) structures, the resultant NiFe–CeO_x/MOF catalysts all show good catalytic activity toward HB decomposition, showing the universality of the MOF supported NiFe–CeO_x catalysts.     

AuPd–MnOx/MOF–Graphene: An Efficient Catalyst for Hydrogen Production from Formic Acid at Room Temperature

The safe and efficient storage and release of hydrogen are widely recognized as the main challenges for the establishment of a fuel‐cell‐based hydrogen economy. Formic acid (FA) has great potential as a safe and convenient source of hydrogen for fuel cells. Despite tremendous efforts, the development of heterogeneous catalysts with high activity and relatively low cost remains a major challenge. The synthesis of AuPd–MnO_x nanocomposite immobilized on ZIF‐8–reduced‐graphene‐oxide (ZIF‐8–rGO) bi‐support by a wet‐chemical method is reported here. Interestingly, the resultant AuPd–MnO_x/ZIF‐8–rGO shows excellent catalytic activity for the generation of hydrogen from FA, and the initial turnover frequency (TOF) reaches a highest value of 382.1 mol H₂ mol catalyst^?1 h^?1 without any additive at 298 K. This good performance of AuPd–MnO_x/ZIF‐8–rGO results from the modified electronic structure of Pd in the AuPd–MnO_x/ZIF‐8–rGO composite, the small size and high dispersion of the AuPd–MnO_x nanocomposite, and also the strong metal‐support interaction between the AuPd–MnO_x and ZIF‐8–rGO bi‐support.     

Boron Nanoparticles for Room‐Temperature Hydrogen Generation from Water

Boron nanoparticles (BNPs) are of great interest for applications such as neutron capture therapy of cancer cells, hydrogen generation from water, and high energy density fuels. Boron is particularly interesting for chemical water splitting, because of its high gravimetric hydrogen generation potential of 277 g H₂ per kg B. However, only a few studies of water splitting by reaction with boron are available, and those have used high temperature steam with external heating. Room‐temperature boron hydrolysis is of great interest from both scientific and practical perspectives. The studies presented here demonstrate that high purity amorphous BNPs can be oxidized by water to produce H₂ at room temperature, without external energy input, in the presence of catalytic quantities of an alkali metal or alkali metal hydride. The BNPs are produced in a single step gas phase process via CO₂ laser‐induced pyrolysis of mixtures of B₂H₆ and SF₆. The BNPs are spherical with a primary particle diameter of 10–15 nm, narrow size distribution, and specific surface area exceeding 250 m² g^?1. This first demonstration of room‐temperature chemical splitting of liquid water using boron opens up exciting new possibilities for on‐demand hydrogen generation at high gravimetric capacity.     

SBA immobilized phosphomolybdic acid: Efficient hybrid mesostructured heterogeneous catalysts

SBA-15 and SBA-3 mesoporous silicas are synthesised by P123 and CTAB surfactants via hydrothermal and liquid phase deposition procedures, respectively. An inorganic-organic hybrid mesoporous material is then synthesised by functionalization of SBA-15 with aminopropyl functional groups via grafting method. After characterization, effect of immobilizing support and functional groups on intercalation of phosphomolybdic acid (H₃PMo₁₂O₄₀) is taken into consideration. The immobilization pattern is discussed and supported H₃PMo₁₂O₄₀ catalysts are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), EDX, inductively coupled plasma (ICP), FT-IR, and UV-vis analysis. The newly synthesised hybrid catalysts are investigated for epoxidation of cyclooctene in presence of hydrogen peroxide as oxidant. The reaction mechanism is discussed. Furthermore, effects of different immobilizing supports and functionalization on catalyst activity, stability, and reusability are taken into consideration. Similar catalytic reactions are carried out with pristine supports and neat H₃PMo₁₂O₄₀ (homogeneous). Results reveal that the mesostructured phosphomolybdic acid based catalysts are shown to be efficient and selective heterogeneous catalysts for oxidation of alkenes.     

Unsaturated Sulfur Edge Engineering of Strongly Coupled MoS2 Nanosheet–Carbon Macroporous Hybrid Catalyst for Enhanced Hydrogen Generation

The low hydrogen adsorption free energy and strong acid/alkaline resistance of layered MoS₂ render it an excellent pH‐universal electrocatalyst for hydrogen evolution reaction (HER). However, the catalytic activity is dominantly suppressed by its limited active‐edge‐site density. Herein, a new strategy is reported for making a class of strongly coupled MoS₂ nanosheet–carbon macroporous hybrid catalysts with engineered unsaturated sulfur edges for boosting HER catalysis by controlling the precursor decomposition and subsequent sodiation/desodiation. Both surface chemical state analysis and first‐principles calculations verify that the resultant catalysts exhibit a desirable valence‐electron state with high exposure of unsaturated sulfur edges and an optimized hydrogen adsorption free energy, significantly improving the intrinsic HER catalytic activity. Such an electrocatalyst exhibits superior and stable catalytic activity toward HER with small overpotentials of 136 mV in 0.5 m H₂SO₄ and 155 mV in 1 m KOH at 10 mA cm^?2, which is the best report for MoS₂–C hybrid electrocatalysts to date. This work paves a new avenue to improve the intrinsic catalytic activity of 2D materials for hydrogen generation.     

Hydride‐Enhanced CO2 Methanation: Water‐Stable BaTiO2.4H0.6 as a New Support

Catalytic CO₂ hydrogenation to CH₄ provides a promising approach to producing natural gas, and reducing the emissions of global CO₂. However, the efficiency of catalytic CO₂ methanation is limited by slow kinetics at low temperatures. This study first demonstrates that an air‐ and water‐stable perovskite oxyhydride BaTiO_2.4H_0.6 could function as an active support material for Ni‐, Ru‐based catalysts for CO₂ methanation at 300–350 °C, a relatively lower temperature. With the oxyhydride support, the activity for Ni and Ru increases by a factor of 2–7 when compared to the BaTiO₃ oxide support. Kinetic analysis shows reduced H₂ poisoning probably due to spillover, implying that the activity change is due to the kinetics being influenced by hydride. Furthermore, the oxyhydride‐supported Ni catalyst is also durable with its catalytic performance preserved for at least 10 h under a humid environment at elevated temperatures. It is anticipated that these perovskite oxyhydrides will shed new light on the design of high‐efficiency metal‐based catalysts for water‐involved catalytic reactions.     

Rational Design of Novel Catalysts with Atomic Layer Deposition for the Reduction of Carbon Dioxide

Carbon dioxide (CO₂) is one of the end products of fuel combustion and the major component of the greenhouse gases. The reduction of atmospheric CO₂ not only decreases environmental pollution but also produces value‐added chemicals, solving energy and environment issues simultaneously. One significant challenge is the low conversion efficiency of CO₂ reduction due to the inertness of the CO₂ molecule. The design of the catalyst nanomaterials with the high selectivity, stability, and the activation capabilities for the conversion of CO₂ is needed. Atomic layer deposition (ALD), capable of constructing catalysts with atomic‐level precision in a highly controllable manner, is a promising technique to address the key problems in CO₂ reduction. This review explores the application of ALD in CO₂ reduction, emphasizing the designs of the efficient catalyst nanomaterials fabricated by the ALD technique and their applications in CO₂ reduction and capture. The significance of the ALD catalysts with the fine structures is highlighted to obtain a better understanding of the catalytic performance–aimed benefits as well as an outlook on the ALD‐designed catalysts for the reduction of CO₂.     

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO2 Batteries

With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO₂ battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO₂ battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li₂CO₃/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g^?1 at a current density of 400 mA g^?1, the cycling performance of the Li–CO₂ battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO₂ batteries as well as other rechargeable metal–gas batteries.     

Highly Efficient Ambient Temperature CO2 Photomethanation Catalyzed by Nanostructured RuO2 on Silicon Photonic Crystal Support

Sunlight‐driven catalytic hydrogenation of CO₂ is an important reaction that generates useful chemicals and fuels and if operated at industrial scales can decrease greenhouse gas CO₂ emissions into the atmosphere. In this work, the photomethanation of CO₂ over highly dispersed nanostructured RuO₂ catalysts on 3D silicon photonic crystal supports, achieving impressive conversion rates as high as 4.4 mmol g_cat^?1 h^?1 at ambient temperatures under high‐intensity solar simulated irradiation, is reported. This performance is an order of magnitude greater than photomethanation rates achieved over control samples made of nanostructured RuO₂ on silicon wafers. The high absorption and unique light‐harvesting properties of the silicon photonic crystal across the entire solar spectral wavelength range coupled with its large surface area are proposed to be responsible for the high methanation rates of the RuO₂ photocatalyst. A density functional theory study on the reaction of CO₂ with H₂ revealed that H₂ splits on the surface of the RuO₂ to form hydroxyl groups that participate in the overall photomethanation process.     

Uncovering Atomic‐Scale Stability and Reactivity in Engineered Zinc Oxide Electrocatalysts for Controllable Syngas Production

In this study, scalable, flame spray synthesis is utilized to develop defective ZnO nanomaterials for the concurrent generation of H₂ and CO during electrochemical CO₂ reduction reactions (CO₂RR). The designed ZnO achieves an H₂/CO ratio of ≈1 with a large current density (j) of 40 mA cm^?2 during long‐term continuous reaction at a cell voltage of 2.6 V. Through in situ atomic pair distribution function analysis, the remarkable stability of these ZnO structures is explored, addressing the knowledge gap in understanding the dynamics of oxide catalysts during CO₂RR. Through optimization of synthesis conditions, ZnO facets are modulated which are shown to affect reaction selectivity, in agreement with theoretical calculations. These findings and insights on synthetic manipulation of active sites in defective metal‐oxides can be used as guidelines to develop active catalysts for syngas production for renewable power‐to‐X to generate a range of fuels and chemicals.     

Recent Trends,Benchmarking, and Challenges of Electrochemical Reduction of CO2 by Molecular Catalysts

CO₂ reduction using molecular catalysts is a key area of study for achieving electrical‐to‐chemical energy storage and feedstock chemical synthesis. Compared to classical metallic solid‐state catalysts, these molecular catalysts often result in high performance and selectivity, even under unfavorable aqueous environments. This review considers the recent state‐of‐the‐art molecular catalysts for CO₂ electroreduction and explains the observed performance, therefore guiding the design principles for the next generation of molecules and material/molecule hybrid electrodes. The most recent advances related to these issues are discussed.     

Doped‐MoSe2 Nanoflakes/3d Metal Oxide–Hydr(Oxy)Oxides Hybrid Catalysts for pH‐Universal Electrochemical Hydrogen Evolution Reaction

Clean hydrogen production is highly promising to meet future global energy demands. The design of earth‐abundant materials with both high activity for hydrogen evolution reaction (HER) and electrochemical stability in both acidic and alkaline environments is needed, in order to enable practical applications. Here, the authors report a non‐noble 3d metal Cl‐chemical doping of liquid phase exfoliated single‐/few‐layer flakes of MoSe₂ for creating MoSe₂/3d metal oxide–hydr(oxy)oxide hybrid HER‐catalysts. It is proposed that the electron‐transfer from MoSe₂ nanoflakes to metal cations and the chlorine complexation‐induced neutralization, as well as the in situ formation of metal oxide–hydr(oxy)oxides on the MoSe₂ nanoflakes' surface, tailor the proton affinity of the catalysts, increasing the number and HER‐kinetics of their active sites in both acidic and alkaline electrolytes. The electrochemical coupling between doped‐MoSe₂/metal oxide–hydr(oxy)oxide hybrids and single‐walled carbon nanotubes heterostructures further accelerates the HER process. Lastly, monolithic stacking of multiple heterostructures is reported as a facile electrode assembly strategy to achieve overpotential for a cathodic current density of 10 mA cm^?2 of 0.081 and 0.064 V in 0.5 m H₂SO₄ and 1 m KOH, respectively. This opens up new opportunities to address the current density versus overpotential requirements targeted in pH‐universal hydrogen production.     

Electrocatalytic Reduction of Gaseous CO2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes

Earth‐abundant Sn/Cu catalysts are highly selective for the electrocatalytic reduction of CO₂ to CO in aqueous electrolytes. However, CO₂ mass transport limitations, resulting from the low solubility of CO₂ in water, so far limit the CO partial current density for Sn/Cu catalysts to about 10 mA cm^?2. Here, a freestanding gas diffusion electrode design based on Sn‐decorated Cu‐coated electrospun polyvinylidene fluoride nanofibers is demonstrated. The use of gaseous CO₂ as a feedstock alleviates mass transport limitations, resulting in high CO partial current densities above 100 mA cm^?2, while maintaining high CO faradaic efficiencies above 80%. These results represent an important step toward an economically viable pathway to CO₂ reduction.     

Application of Gibbs Ensemble and NPT Monte Carlo Simulation to the Development of Improved Processes for H2S-rich Gases

The design of improved processes for producing hydrogen sulphide (H₂S)-rich natural gases faces a general scarcity of experimental data, because of the high toxicity and corrosive character of H₂S. We present here a prospective application of Monte Carlo simulation to predict desired fluid properties.

A first step was the selection of intermolecular potentials for water, H₂S, carbon dioxide (CO₂) and methane on the basis of pure component properties (vapour pressures, vapourisation enthalpies, liquid densities, supercritical densities at high pressure). A second step involved the prediction of phase diagrams of binary and ternary mixtures of the methane–H₂S–water system, using two-phase and three-phase Gibbs ensemble simulations. In a third step the density and excess enthalpy of the CO₂–H₂S system were computed for a large range of pressure, temperature and compositions.

Comparison with available experimental data showed that all investigated properties could be consistently predicted without needing parameter calibration on binary data. The results also provided a qualitative understanding of water solubility in H₂S-rich fluids based on molecular self-association.     

Symmetric and Asymmetric Zeolitic Imidazolate Frameworks (ZIFs)/Polybenzimidazole (PBI) Nanocomposite Membranes for Hydrogen Purification at High Temperatures

High‐performance zeolitic imidazolate frameworks (ZIFs)/polybenzimidazole (PBI) nanocomposites are molecularly designed for hydrogen separation at high temperatures, and demonstrate it in a useful configuration as dual‐layer hollow fibers for the first time. By incorporating as‐synthesized nanoporous ZIF‐8 nanoparticles into the high thermal stability but extremely low permeability polybenzimidazole (PBI), the resultant mixed matrix membranes show an impressive enhancement in H₂ permeability as high as a hundred times without any significant deduction in H₂/CO₂ selectivity. The 30/70 ZIF‐8/PBI dense membrane has a H₂ permeability of 105.4 Barrer and a H₂/CO₂ selectivity of 12.3. This performance is far superior to ZIF‐7/PBI membranes and is the best ever reported data for H₂‐selective polymeric materials in the literature. Meanwhile, defect‐free ZIF‐8‐PBI/Matrimid dual‐layer hollow fibers are successfully fabricated, without post‐annealing and coating, by optimizing ZIF‐8 nanoparticle loadings, spinning conditions, and solvent‐exchange procedures. Two types of hollow fibers targeted at either high H₂/CO₂ selectivity or high H₂ permeance are developed: i) PZM10‐I B fibers with a medium H₂ permeance of 64.5 GPU (2.16 ×10^?8 mol m^?2 s^?1 Pa^?1) at 180°C and a high H₂/CO₂ selectivity of 12.3, and, ii) PZM33‐I B fibers with a high H₂ permeance of 202 GPU (6.77 ×10^?8 mol m^?2 s^?1 Pa^?1) at 180°C and a medium H₂/CO₂ selectivity of 7.7. This work not only molecularly designs novel nanocomposite materials for harsh industrial applications, such as syngas and hydrogen production, but also, for the first time, synergistically combines the strengths of both ZIF‐8 and PBI for energy‐related applications.     

Polyoxometalate‐Derived Ultrasmall Pt2W/WO3 Heterostructure Outperforms Platinum for Large‐Current‐Density H2 Evolution

Platinum (Pt)‐based catalysts with high Pt utilization efficiency for efficient H₂ evolution are attracting extensive attention to meet the issues of energy exhaustion and environmental pollution. Herein, a one‐step electrochemical method is demonstrated to construct ultrafine heterostructure Pt₂W/WO₃ on reduced graphene oxide (RGO) by injecting multielectrons into the Preyssler anion [NaP₅W₃₀O₁₁₀]^14? to codeposit with anodic deliquescent Pt cations. The resulting Pt₂W/WO₃/RGO shows much higher performance than that of commercial Pt catalysts for large‐current‐density H₂ evolution, which can deliver a large current density of 500 mA cm^?2 with an overpotential of only 394 mV, much lower than that of 20% Pt/C (578 mV). Comparisons with control experiments and density functional theory (DFT) calculations both suggest that the much enhanced activity can be mainly attributed to the synergistic cooperation of different components to drive fast and continuous hydrogen desorption on Pt₂W/WO₃/RGO, while it could not run normally for 20% Pt/C under similar conditions due to the formation of huge bubbles on the electrode surface. The effective integration of high catalytic activity and hydrogen desorption ability into a single material can yield advanced materials for large‐current‐density H₂ evolution with remarkable stability.     

High light‐induced hydrogen peroxide production in Chlamydomonas reinhardtii is increased by high CO2 availability

The production of reactive oxygen species (ROS) is an unavoidable part of photosynthesis. Stress that accompanies high light levels and low CO₂ availability putatively includes enhanced ROS production in the so‐called Mehler reaction. Such conditions are thought to encourage O₂ to become an electron acceptor at photosystem I, producing the ROS superoxide anion radical () and hydrogen peroxide (H₂O₂). In contrast, here it is shown in Chlamydomonas reinhardtii that CO₂ depletion under high light levels lowered cellular H₂O₂ production, and that elevated CO₂ levels increased H₂O₂ production. Using various photosynthetic and mitochondrial mutants of C. reinhardtii, the chloroplast was identified as the main source of elevated H₂O₂ production under high CO₂ availability. High light levels under low CO₂ availability induced photoprotective mechanisms called non‐photochemical quenching, or NPQ, including state transitions (qT) and high energy state quenching (qE). The qE‐deficient mutant npq4 produced more H₂O₂ than wild‐type cells under high light levels, although less so under high CO₂ availability, whereas it demonstrated equal or greater enzymatic H₂O₂‐degrading capacity. The qT‐deficient mutant stt7‐9 produced the same H₂O₂ as wild‐type cells under high CO₂ availability. Physiological levels of H₂O₂ were able to hinder qT and the induction of state 2, providing an explanation for why under high light levels and high CO₂ availability wild‐type cells behaved like stt7‐9 cells stuck in state 1.     

Free-standing Stanene for High Selectivity of Formate in Electrocatalytic Carbon Dioxide Reduction Reaction

As well-known electrocatalysts with good catalytic efficiency for carbon dioxide reduction reaction (CO₂RR) towards the production of formate, tin (Sn)-based catalysts have aroused broad concern. Here, free-standing porous stanene is synthesized for the first time by a facile wet chemical method, and its excellent electrocatalytic performance for formate (HCOO⁻) formation in CO₂RR is demonstrated. High Faradaic efficiency (F.E., 93% at −930 mV versus reversible hydrogen electrode (RHE)) can be achieved in the CO₂RR catalyzed by stanene in 0.5 m KHCO₃ aqueous solution. The in situ Mössbauer spectra reveal that zero-valent Sn aids in improving the selectivity of formate production. Furthermore, density functional theory calculations suggest that the high selectivity of HCOO⁻ of CO₂RR on stanene mainly originates from the edge sites on Sn (100). To further explore the practicability of the stanene-based catalysts for CO₂RR, stanene decorated by 3 wt% BP-2000 is prepared, showing an excellent F.E. of 98% at −930 mV versus RHE due to the higher exposure of catalytic active sites. These new findings of the activity origination and reaction mechanism of stanene contribute to the deeper understanding of Sn-based catalysts for CO₂RR, which is beneficial for the future designation of highly efficient CO₂RR catalysts.