Photocatalytic hydrogen evolution is an environmentally friendly means of energy generation. Although g-C3N4 possesses fascinating features, its inherent shortcomings limit its photocatalytic applications. Therefore, modifying the intrinsic properties of g-C3N4 and introducing cocatalysts are essential to ameliorate the photocatalytic efficiency. To achieve this, metal-like Ti3C2Tx is integrated with crystalline g-C3N4 via a combined salt-assisted and freeze-drying approach to form crystalline g-C3N4/Ti3C2Tx (CCN/TCT) hybrids with different Ti3C2Tx loading amounts (0, 0.2, 0.3, 0.4, 0.5, 1, 5, 10 wt.%). Benefiting from the crystallization of CN, as evidenced by the XRD graph, and the marvelous conductivity of Ti3C2Tx supported by EIS plots, CCN/TCT/Pt loaded with 0.5 wt.% Ti3C2Tx displays an elevated H2 (2) should be subscripted evolution rate of 2651.93 µmol g-1 h-1 and a high apparent quantum efficiency of 7.26% (420 nm), outperforming CN/Pt, CCN/Pt, and other CCN/TCT/Pt hybrids. The enhanced performance is attributed to the synergistic effect of the highly crystalline structure of CCN that enables fleet charge transport and the efficient dual cocatalysts, Ti3C2Tx and Pt, that foster charge separation and provide plentiful active sites. This work demonstrates the potential of CCN/TCT as a promising material for hydrogen production, suggesting a significant advancement in the design of CCN heterostructures for effective photocatalytic systems.
A strategic roadmap for noncarbonized fuels is a global priority, and the reduction of carbon dioxide emissions is a key focus of the Paris Agreement to mitigate the effects of rising temperatures. In this context, hydrogen is a promising noncarbonized fuel, but the pace of its implementation will depend on the engineering advancements made at each step of its value chain. To accelerate its adoption, various applications of hydrogen across industries, transport, power, and building sectors have been identified, where it can be used as a feedstock, fuel, or energy carrier and storage. However, widespread usage of hydrogen will depend on its political, industrial, and social acceptance. It is essential to carefully assess the hydrogen value chain and compare it with existing solar technologies. The major challenge to widespread adoption of hydrogen is its cost as outlined in the roadmap for hydrogen. It needs to be produced at the levelized cost of hydrogen of less than $2 kg-1 to be competitive with the established process of steam methane reforming. Therefore, this review provides a comprehensive analysis of each step of the hydrogen value chain, outlining both the current challenges and recent advances.
Semiconductor-based materials utilized in photocatalysts and electrocatalysts present a sophisticated solution for efficient solar energy utilization and bias control, a field extensively explored for its potential in sustainable energy and environmental management. Recently, 3D printing has emerged as a transformative technology, offering rapid, cost-efficient, and highly customizable approaches to designing photocatalysts and electrocatalysts with precise structural control and tailored substrates. The adaptability and precision of printing facilitate seamless integration, loading, and blending of diverse photo(electro)catalytic materials during the printing process, significantly reducing material loss compared to traditional methods. Despite the evident advantages of 3D printing, a comprehensive compendium delineating its application in the realm of photocatalysis and electrocatalysis is conspicuously absent. This paper initiates by delving into the fundamental principles and mechanisms underpinning photocatalysts electrocatalysts and 3D printing. Subsequently, an exhaustive overview of the latest 3D printing techniques, underscoring their pivotal role in shaping the landscape of photocatalysts and electrocatalysts for energy and environmental applications. Furthermore, the paper examines various methodologies for seamlessly incorporating catalysts into 3D printed substrates, elucidating the consequential effects of catalyst deposition on catalytic properties. Finally, the paper thoroughly discusses the challenges that necessitate focused attention and resolution for future advancements in this domain.
The extensive examination of hexagonal molybdenum carbide (ß-Mo2C) as a non-noble cocatalyst in the realm of photocatalytic H2 evolution is predominantly motivated by its exceptional capacity to adsorb H+ ions akin to Pt and its advantageous conductivity characteristics. However, the H2 evolution rate of photocatalysts modified with ß-Mo2C is limited as a result of their comparatively low ability to release H through desorption. Therefore, a facile method was employed to synthesize carbon intercalated dual phase molybdenum carbide (MC@C) quantum dots (ca. 3.13 nm) containing both α-MoC and ß-Mo2C decorated on g-C3N4 (gCN). The synthesis process involved a simple and efficient combination of sonication-assisted self-assembly and calcination techniques. 3-MC@C/gCN exhibited the highest efficiency in generating H2, with a rate of 4078 µmol g-1h-1 under 4 h simulated sunlight irradiation, which is 13 times higher than pristine gCN. Furthermore, from the cycle test, 3-MC@C/gCN showcased exceptional photochemical stability of 65 h, as it maintained a H2 evolution rate of 40 mmol g-1h-1. The heightened level of activity observed in the 3-MC@C/gCN system can be ascribed to the synergistic effects of MoC-Mo2C that arise due to the existence of a carbon layer. The presence of a carbon layer enhanced the transmission of photoinduced electrons, while the MoC-Mo2C@C composite served as active sites, thereby facilitating the H2 production reaction of gCN. The present study introduces a potentially paradigm-shifting concept pertaining to the exploration of novel Mo-based cocatalysts with the aim of augmenting the efficacy of photocatalytic H2 production.
Photocatalytic technology has been well studied as a means to achieve sustainable energy generation through water splitting or chemical synthesis. Recently, a low C/N atomic ratio carbon nitride allotrope, C3N5, has been found to be highly prospective due to its excellent electronic properties and ample N-active sites compared to g-C3N4. Tangentially, crystalline g-C3N4 has also been a prospective candidate due to its improved electron transport and extended π-conjugated system. For the first time, our group successfully employed a one-step molten salt calcination method to prepare novel N-rich crystalline C3N5 and elucidate the effect of calcination temperature on the heptazine/triazine phase. Calcination temperatures of 500 °C (CC3N5-500) and 550 °C (CC3N5-550) lead to crystalline carbon nitride with both heptazine and triazine phases, forming an intimate isotype heterojunction for robust interfacial charge separation. An excellent photocatalytic hydrogen evolution rate (359.97 µmol h-1; apparent quantum efficiency (AQE): 12.86% at 420 nm) was achieved using CC3N5-500, which was 15-fold higher than that of pristine C3N5. Furthermore, CC3N5-500 exhibited improved activity for simultaneous benzyl alcohol oxidation and hydrogen production, as well as H2O2 production (AQE: 9.49% at 420 nm), signifying its multitudinous photoredox capabilities. Moreover, the recyclability tests of the optimal CC3N5-500 on a 3D-printed substrate also showed a 92% performance retention after 4 cycles (16 h). This highlights that crystalline C3N5 significantly augmented the reaction performance for diverse multifunctional solar-driven applications. As such, these results serve as a guide toward the structural tuning of 2D metal-free carbon nanomaterials with tunable crystallinity toward achieving boosted photocatalysis.
Energy security concerns require novel greener and more sustainable processes, and Paris Agreement goals have put in motion several measures aligned with the 2050 roadmap strategies and net zero emission goals. Renewable energies are a promising alternative to existing infrastructures, with solar energy one of the most appealing due to its use of the overabundant natural source of energy. Photocatalysis as a simple heterogeneous surface catalytic reaction is well placed to enter the realm of scaling up processes for wide scale implementation. Inspired by natural photosynthesis, artificial water splitting's beauty lies in its simplicity, requiring only light, a catalyst, and water. The bottlenecks to producing a high volume of hydrogen are several: Reactors with efficient photonic/mass/heat profiles, multifunctional efficient solar-driven catalysts, and proliferation of pilot devices. Three case studies, developed in Japan, Spain, and France are showcased to emphasize efforts on a pilot and large-scale examples. In order for solar-assisted photocatalytic H2 to mature as a solution, the aforementioned bottlenecks must be overcome for the field to advance its technology readiness level, assess the capital expenditure, and enter the market.
The electro/photocatalytic CO2 reduction reaction (CO2RR) is a long-term avenue toward synthesizing renewable fuels and value-added chemicals, as well as addressing the global energy crisis and environmental challenges. As a result, current research studies have focused on investigating new materials and implementing numerous fabrication approaches to increase the catalytic performances of electro/photocatalysts toward the CO2RR. MXenes, also known as 2D transition metal carbides, nitrides, and carbonitrides, are intriguing materials with outstanding traits. Since their discovery in 2011, there has been a flurry of interest in MXenes in electrocatalysis and photocatalysis, owing to their several benefits, including high mechanical strength, tunable structure, surface functionality, high specific surface area, and remarkable electrical conductivity. Herein, this review serves as a milestone for the most recent development of MXene-based catalysts for the electrocatalytic and photocatalytic CO2RR. The overall structure of MXenes is described, followed by a summary of several synthesis pathways classified as top-down and bottom-up approaches, including HF-etching, in situ HF-formation, electrochemical etching, and halogen etching. Additionally, the state-of-the-art development in the field of both the electrocatalytic and photocatalytic CO2RR is systematically reviewed. Surface termination modulation and heterostructure engineering of MXene-based electro/photocatalysts, and insights into the reaction mechanism for the comprehension of the structure-performance relationship from the CO2RR via density functional theory (DFT) have been underlined toward activity enhancement. Finally, imperative issues together with future perspectives associated with MXene-based electro/photocatalysts are proposed.
Invited for this month's cover is the group of Prof. Dr. Wee-Jun Ong at Xiamen University Malaysia. The image shows a model of Xiamen University and is in celebration of the 5th and 100th anniversary of Xiamen University Malaysia and Xiamen University, respectively. The cover showcases the institutes as a pillar of renewable nanotechnology research and a key player in the ever-growing search for sustainable energy. The Research Article itself is available at 10.1002/cssc.202200857.
Carbon Dioxide , Formates , Animals , Ethylenes , Humans , Life Cycle Stages
Converting CO2 into valuable C1 -C2 chemicals through electrochemical CO2 reduction (ECR) has potential to remedy the ever-increasing climate problems owing to the intensification of industrial activity. In this work, cradle-to-gate life cycle assessment (LCA) was performed to quantify the environmental impacts of formic acid (FA) and ethylene production through ECR benchmarked with the conventional processes. At the midpoint level, global warming potential (GWP) effects of FA and ethylene production through ECR recorded 5.6 and 1.6-times that of the conventional process, respectively. Although ECR currently has limited environmental benefits, the incorporation of hydropower has vast potential after evaluating four sustainable electricity sources, namely hydropower, wind, solar, and biomass. Notably, ECR to FA recorded a 24 % reduction in petrochemical usage. For ethylene production, human health damage, ecosystem damage, and petrochemical use were reduced by 67, 94, and 110 %, respectively. Sensitivity analysis indicated that a sustainable energy supply chain for ECR will accelerate the development of a circular economy.
Carbon Dioxide , Ecosystem , Animals , Ethylenes , Formates , Humans , Life Cycle Stages
Unique performance of the hybrid organic-inorganic halide perovskites (HOIPs) has attracted great attention because of their continuous exploration and breakthrough in a multitude of energy-related applications. However, the instability and lead-induced toxicity that arise in bulk perovskites are the two major challenges that impede their future commercialization process. To find a solution, a series of two-dimensional HOIPs (2D HOIPs) are investigated to prolong the device lifetime with highly efficient photoelectric conversion and energy storage. Herein, the recent advances of 2D HOIPs and their structural derivatives for the energy realms are summarized and discussed. The basic understanding of crystal structures, physicochemical properties, and growth mechanisms is presented. In addition, the current challenges and future directions to provide a roadmap for the development of next generation 2D HOIPs are prospected.
Dry adhesives that combine strong adhesion, high transparency, and reusability are needed to support developments in emerging fields such as medical electrodes and the bonding of electronic optical devices. However, achieving all of these features in a single material remains challenging. Herein, we propose a pressure-responsive polyurethane (PU) adhesive inspired by the octopus sucker. This adhesive not only showcases reversible adhesion to both solid materials and biological tissues but also exhibits robust stability and high transparency (>90%). As the adhesive strength of the PU adhesive corresponds to the application force, adhesion could be adjusted by the preloading force and/or pressure. The adhesive exhibits high static adhesion (â¼120 kPa) and 180° peeling force (â¼500 N/m), which is far stronger than those of most existing artificial dry adhesives. Moreover, the adhesion strength is effectively maintained even after 100 bonding-peeling cycles. Because the adhesive tape relies on the combination of negative pressure and intermolecular forces, it overcomes the underlying problems caused by glue residue like that left by traditional glue tapes after removal. In addition, the PU adhesive also shows wet-cleaning performance; the contaminated tape can recover 90-95% of the lost adhesion strength after being cleaned with water. The results show that an adhesive with a microstructure designed to increase the contribution of negative pressure can combine high reversible adhesion and long fatigue life.
Biomimetic Materials , Biomimetics , Adhesiveness , Adhesives , Water
In this work, a series of non-noble metal single-atom catalysts of Mo2 CS2 -MXene for CO2 reduction were systematically investigated by well-defined density-functional-theory (DFT) calculations. It is found that nine types of transitional metal (TM) supported Mo2 CS2 (TM-Mo2 CS2 ) are very stable, while eight can effectively inhibit the competitive hydrogen evolution reaction (HER). After comprehensively comparing the changes of free energy for each pathway in CO2 reduction reaction (CO2 RR), it is found that the products of TM-Mo2 CS2 are not completely CH4 . Furthermore, Cr-, Fe-, Co- and Ni-Mo2 CS2 are found to render excellent CO2 RR catalytic activity, and their limiting potentials are in the range of 0.245-0.304â V. In particular, Fe-Mo2 CS2 with a nitrogenase-like structure has the lowest limiting potential and the highest electrocatalytic activity. Ab initio molecular dynamics (AIMD) simulations have also proven that these kinds of single-atom catalysts with robust performance could exist stably at room temperature. Therefore, these single TM atoms anchored on the surface of MXenes can be profiled as a promising catalyst for the electrochemical reduction of CO2 .
This study aimed to analyze the environmental impacts of the oxidative desulfurization (ODS) process catalyzed by metal-free reduced graphene oxide (rGO) through life cycle assessment (LCA). The environmental impacts study containing the rGO production process, the ODS process, the comparison of different oxidants and solvents was developed. This study was performed by using ReCiPe 2016 V1.03 Hierarchist midpoint as well as endpoint approach and SimaPro software. For the production of 1 kg rGO, the results showed that hydrochloric acid (washing), sulfuric acid (mixing), hydrazine (reduction) and electricity were four main contributors in this process, and this process showed a significant impact on human health 14.21 Pt followed by ecosystem 0.845 Pt and resources 0.164 Pt. For the production of 1 kg desulfurized oil (400 ppm), main environmental impacts were terrestrial ecotoxicity (43.256 kg 1,4-DCB), global warming (41.058 kg CO2), human non-carcinogenic toxicity (19.570 kg 1,4-DCB) and fossil resource scarcity (13.178 kg oil), and the main contributors were electricity, diesel oil and acetonitrile. The whole ODS process also showed a greatest effect on human health. For two common oxidants hydrogen peroxide and oxygen used in ODS, hydrogen peroxide showed a greater impact than oxygen. On the other hand, for three common solvents employed in ODS, N-methyl-2-pyrrolidone had a more serious impact on human health followed by acetonitrile and N,N-dimethylformamide. As such, LCA results demonstrated the detailed environmental impacts originated from the catalytic ODS, hence elucidating systematic guidance for its future development toward practicality.
Ecosystem , Gasoline , Animals , Catalysis , Graphite , Humans , Life Cycle Stages , Oxidative Stress
A fully integrated, flexible, and functional sensing device for exhaled breath analysis drastically transforms conventional medical diagnosis to non-invasive, low-cost, real-time, and personalized health care. 2D materials based on MXenes offer multiple advantages for accurately detecting various breath biomarkers compared to conventional semiconducting oxides. High surface sensitivity, large surface-to-weight ratio, room temperature detection, and easy-to-assemble structures are vital parameters for such sensing devices in which MXenes have demonstrated all these properties both experimentally and theoretically. So far, MXenes-based flexible sensor is successfully fabricated at a lab-scale and is predicted to be translated into clinical practice within the next few years. This review presents a potential application of MXenes as emerging materials for flexible and wearable sensor devices. The biomarkers from exhaled breath are described first, with emphasis on metabolic processes and diseases indicated by abnormal biomarkers. Then, biomarkers sensing performances provided by MXenes families and the enhancement strategies are discussed. The method of fabrications toward MXenes integration into various flexible substrates is summarized. Finally, the fundamental challenges and prospects, including portable integration with Internet-of-Thing (IoT) and Artificial Intelligence (AI), are addressed to realize marketization.
Smart Materials , Wearable Electronic Devices , Artificial Intelligence , Biomarkers , Breath Tests , Humans
The ceaseless increase of pollution cases due to the tremendous consumption of fossil fuels has steered the world towards an environmental crisis and necessitated urgency to curtail noxious sulfur oxide emissions. Since the world is moving toward green chemistry, a fuel desulfurization process driven by clean technology is of paramount significance in the field of environmental remediation. Among the novel desulfurization techniques, the oxidative desulfurization (ODS) process has been intensively studied and is highlighted as the rising star to effectuate sulfur-free fuels due to its mild reaction conditions and remarkable desulfurization performances in the past decade. This critical review emphasizes the latest advances in thermal catalytic ODS and photocatalytic ODS related to the design and synthesis routes of myriad materials. This encompasses the engineering of metal oxides, ionic liquids, deep eutectic solvents, polyoxometalates, metal-organic frameworks, metal-free materials and their hybrids in the customization of advantageous properties in terms of morphology, topography, composition and electronic states. The essential connection between catalyst characteristics and performances in ODS will be critically discussed along with corresponding reaction mechanisms to provide thorough insight for shaping future research directions. The impacts of oxidant type, solvent type, temperature and other pivotal factors on the effectiveness of ODS are outlined. Finally, a summary of confronted challenges and future outlooks in the journey to ODS application is presented.
Graphitic carbon nitride (g-C3 N4 ) is a kind of ideal metal-free photocatalysts for artificial photosynthesis. At present, pristine g-C3 N4 suffers from small specific surface area, poor light absorption at longer wavelengths, low charge migration rate, and a high recombination rate of photogenerated electron-hole pairs, which significantly limit its performance. Among a myriad of modification strategies, point-defect engineering, namely tunable vacancies and dopant introduction, is capable of harnessing the superb structural, textural, optical, and electronic properties of g-C3 N4 to acquire an ameliorated photocatalytic activity. In view of the burgeoning development in this pacey field, a timely review on the state-of-the-art advancement of point-defect engineering of g-C3 N4 is of vital significance to advance the solar energy conversion. Particularly, insights into the intriguing roles of point defects, the synthesis, characterizations, and the systematic control of point defects, as well as the versatile application of defective g-C3 N4 -based nanomaterials toward photocatalytic water splitting, carbon dioxide reduction and nitrogen fixation will be presented in detail. Lastly, this review will conclude with a balanced perspective on the technical and scientific hindrances and future prospects. Overall, it is envisioned that this review will open a new frontier to uncover novel functionalities of defective g-C3 N4 -based nanostructures in energy catalysis.
Graphite , Catalysis , Nitrogen Compounds , Photosynthesis
