Water electrolysis holds great potential as a method for producing renewable hydrogen fuel at large-scale, and to replace the fossil fuels responsible for greenhouse gases emissions and global climate change. To reduce the cost of hydrogen and make it competitive against fossil fuels, the efficiency of green hydrogen production should be maximized. This requires superior electrocatalysts to reduce the reaction energy barriers. The development of catalytic materials has mostly relied on empirical, trial-and-error methods because of the complicated, multidimensional, and dynamic nature of catalysis, requiring significant time and effort to find optimized multicomponent catalysts under a variety of reaction conditions. The ultimate goal for all researchers in the materials science and engineering field is the rational and efficient design of materials with desired performance. Discovering and understanding new catalysts with desired properties is at the heart of materials science research. This process can benefit from machine learning (ML), given the complex nature of catalytic reactions and vast range of candidate materials. This review summarizes recent achievements in catalysts discovery for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The basic concepts of ML algorithms and practical guides for materials scientists are also demonstrated. The challenges and strategies of applying ML are discussed, which should be collaboratively addressed by materials scientists and ML communities. The ultimate integration of ML in catalyst development is expected to accelerate the design, discovery, optimization, and interpretation of superior electrocatalysts, to realize a carbon-free ecosystem based on green hydrogen.

Environmental issues such as global warming due to fossil fuel use are now major worldwide concerns, and interest in renewable and clean energy is growing. Of the various types of renewable energy, green hydrogen energy has recently attracted attention because of its eco-friendly and high-energy density. Electrochemical water splitting is considered a pollution-free means of producing clean hydrogen and oxygen and in large quantities. The development of non-noble electrocatalysts with low cost and high performance in water splitting has also attracted considerable attention. In this study, we successfully synthesized a NiCo2O4/NF electrode for an oxygen evolution reaction in alkaline water splitting using a hydrothermal method, which was followed by post-heat treatment. The effects of heat treatment on the electrochemical performance of the electrodes were evaluated under different heat-treatment conditions. The optimized NCO/NF-300 electrode showed an overpotential of 416 mV at a high current density of 50 mA/cm2 and a low Tafel slope (49.06 mV dec-1). It also showed excellent stability (due to the large surface area) and the lowest charge transfer resistance (12.59 Ω). The results suggested that our noble-metal free electrodes have great potential for use in developing alkaline electrolysis systems.

광전기화학 성능을 향상시키기 위해 각 ZnO, ZnSe과 g-C3N4 소재의 장점을 살리도록 3성분계 적층 구조를 디자 인했다. 용액공정으로 FTO 기판위에서 ZnO 나노로드 어레이가 성장하도록 한 후 ZnO표면에 Se을 부착시켜 ZnO표면에 서 ZnSe층이 형성 되도록 이온 치환법을 도입하였다. ZnO/ZnSe 나노로드 위에 g-C3N4 층을 스핀코팅 한 후 각 층이 화 학적 접합이 되도록 질소 분위기 하에서 열처리를 하였다. AM 1.5G, 0.5 V 외부전압하에서 각 적층구조별로 광전기화학 적 전류밀도를 측정하였고 비교 결과 ZnO/ZnSe/g-C3N4 나노로드가 ZnO 및 ZnO/ZnSe 나노로드에 비하여 보다 높은 광 전류 밀도가 측정되었다. 수직 정렬된 ZnO 육각 프리즘형태는 큰 비표면적과 축 방향을 따라 전자 흐름을 원활히 하고, ZnSe 층은 비표면적과 광흡수 범위를 더욱 넗히는 효과를 가져왔다. 이로 인하여 ZnO/ZnSe/g-C3N4 삼원 접합 전극의 향상된 성능은 가시광선 흡수범위 확장, 전하 분리 강화 및 전자 전도도 향상으로 인한 시너지 효과에 기인되는 것으로 판단된다.

We report on the fabrication and photoelectrochemical(PEC) properties of a Cu2O thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in Cu2O thin film as an efficient photoelectrode for solardriven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated Cu2O/ZnO p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/ZnO photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., 0.77 mA/cm2 at 0.5 V vs Hg/HgCl2 in a 1 mM Na2SO4 electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Hg/ HgCl2, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

We report facile solution processing of mesoporous hematite (α-Fe2O3) thin films for high efficiency solar-driven water splitting. Fe2O3 thin films were prepared on fluorine doped tin oxide(FTO) conducting substrates by spin coating of a precursor solution followed by annealing at 550 oC for 30 min. in air ambient. Specifically, the precursor solution was prepared by dissolving non-toxic FeCl3 as an Fe source in highly versatile dimethyl sulfoxide(DMSO) as a solvent. The as-deposited and annealed thin films were characterized for their morphological, structural and optical properties using field-emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and UV-Vis absorption spectroscopy. The photoelectrochemical performance of the precursor (α-FeOOH) and annealed (α-Fe2O3) films were characterized and it was found that the α-Fe2O3 film exhibited an increased photocurrent density of ~0.78 mA/cm2 at 1.23 V vs. RHE, which is about 3.4 times higher than that of the α-FeOOH films (0.23 mA/cm2 at 1.23 V vs. RHE). The improved performance can be attributed to the improved crystallinity and porosity of α-Fe2O3 thin films after annealing treatment at higher temperatures. Detailed electrical characterization was further carried out to elucidate the enhanced PEC performance of α-Fe2O3 thin films.

We report on the fabrication and characterization of a novel Cu2O/CuO heterojunction structure with CuO nanorods embedded in Cu2O thin film as an efficient photocathode for photoelectrochemical (PEC) solar water splitting. A CuO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method; then, a Cu2O thin film was electrodeposited onto the CuO nanorod array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated Cu2O/CuO heterojunction photocathode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/CuO photocathode was found to exhibit negligible dark current and high photocurrent density, e.g. −1.05 mA/cm2 at −0.6 V vs. Hg/HgCl2 in 1 mM Na2SO4 electrolyte, revealing the effective operation of the oxide heterostructure. The photocurrent conversion efficiency of the Cu2O/CuO photocathode was estimated to be 1.27% at −0.6 V vs. Hg/HgCl2. Moreover, the PEC current density versus time (J-T) profile measured at −0.5 V vs. Hg/HgCl2 on the Cu2O/CuO photocathode indicated a 3-fold increase in the photocurrent density compared to that of a simple Cu2O thin film photocathode. The improved PEC performance was attributed to a certain synergistic effect of the bilayer heterostructure on the light absorption and electron-hole recombination processes.

Quaternary amonium salts are used as anion-exchange and also easily decomposed due to their intrinsic structural instability. These drawbacks have limited the long-term utilization of the membranes. The objectives of this study are to synthesize high performance anion-exchange membranes and to investigate their electrochemical properties The new membranes were prepared via a monomer sorption method. Their morphological and electrochemical properties have been investigated through various analyses. While the accumulated water-splitting flux of the commercial membrane containing conventional quaternary ammonium groups was shown to largely increase with time, theirs of the new membrane was shown without significant change.

설폰화된 Polyetheretherketone 양이온교환막과 TMA 함량에 따라 1:1부터 3:1까지 아민화된 Polysulfone 음이온교환막을 이용하여 바이폴라막을 제조하였다. HCl, NaOH, NaCl을 일정 유량 및 정전류의 조건하에서 순환시키면서 산과 염기의 농도변화를 측정하였다. HCl의 경우 7.1g/L에서 17.3g/L, NaOH는 7.7g/L에서 20.4g/L로 2∼3배 정도 농도가 증가하는 것을 보였다. 아민함량의 증가에 따라 산과 염기의 농도는 증가하는 경향을 나타냈지만, 정전류에 따른 전압은 2:1음이온교환막이 가장 안정된 수치를 나타냈다. 또한, 막의 저항을 줄이기 위해 양이온교환막 표면을 촉매처리하여 실험한 결과, 보다 감소한 전압 값을 관찰할 수 있었다.

본 연구에서는 이온교환막을 이용한 전기화학적 수처리 공정의 효율을 향상시키기 위해 낮은 전기적 저항, 높은이온선택 투과성, 및 농도분극 조건에서 낮은 물분해 플럭스 특성을 갖는 새로운 세공충진 음이온 교환막을 개발하였다. 다공성 폴리올레핀 기재에 이온교환능이 우수한 4급 암모늄기를 포함한 공중합 고분자를 충진하여 상용막 이상의 성능을 갖는 기저 멤브레인을 제조하였다. 또한 기저 막 표면에 이미다졸륨 고분자를 코팅하여 전기화학적 성능을 유지하며 동시에 물분해플럭스를 효과적으로 제어할 수 있음을 확인하였다. 제조된 세공충진 음이온 교환막은 상용막 대비 약 1/6∼1/8 수준의 매우낮은 전기적 저항을 나타내었으며 동시에 농도분극 조건에서 양이온 교환막 수준의 낮은 물분해 플럭스를 나타내었다

Mn-Fe oxide and Mn-Fe oxide/(50wt%/50wt%) were prepared by ball milling method. XRD data of the prepared samples revealed that hematite and ferrite phase coexisted. Water splitting at 1273K, after thermal reduction at 1573K, was performed 4 times for the samples. Hydrogen production amount was analyzed by GC with TCD detector. Water splitting capacity of Mn-Fe oxide was improved by ball milling with .

본 연구에서는 양이온교환막 표면에 형성된 바이폴라 계면이 물분해 현상에 미치는 영향을 조사하였다. 실험결과, 전기투석 중 막표면에 형성된 고정화된 바이폴라 계면이 심각한 물분해를 유발함을 알 수 있었다. 특히, 고정화된 바이폴라 계면은 다가 양이온이 전해질로 이용되는 전기투석 시스템에서 양이온교환막 표면에 쉽게 형성됨을 알 수 있었다. 낮은 용해도적 상수를 갖는 다가 양이온들은 급격한 물분해를 유발하였는데 이는 이들이 막표면에서 쉽게 수산화물의 형태로 침적되며 따라서 수소-친화 그룹과 수산화-친화 그룹으로 구성된 바이폴라 계면이 막-용액 계면에 형성됨을 알 수 있었다. 따라서 물분해는 막 표면의 금속수산화물 층과 막의 고정전하 그룹간에 발생되는 강한 전기장에 의해 크게 활성화됨을 알수 있다. 또한 이와 유사하게 분자량이 큰 유기 상대이온들이 막표면에 누적되는 경우에도 고정화된 바이폴라 계면이 형성되어 한계전류밀도 이상에서 심각한 물분해를 유발하였다. 따라서 전기투석의 고전류 운전시 효율 향상을 위해서는 막표면에 유발되는 고정화된 바이폴라 계면의 형성을 억제하는 것이 매우 중요함을 알 수 있다.

피리디니움 (pyridunium) 그룹을 포함한 음이온교환막의 제조 및 전기화학적 특성 평가를 수행하였다. 실험 결과, 제조된 피리디니움 음이온교환막은 상용막과 대등한 전기저항 (3.0 Xicm2>, in 0.5 mol dm-3 NaCl) 및 높은 이온선택도 (Cl- 이온수송수 약 0.97)의 우수한 전기화학적 특성을 나타내었다. 또한 피리니디움 그룹을 함유한 음이온교환막에서의 물분해는 상용막 (AM-1, Tokuyama Corp., Japan)에 비해 동일한 전류밀도 하에서 약 100배 내지 1000배 가량 낮게 측정되었는데 이는 4차 아로마틱 피리디니움 그룹의 공명효과 (resonance effect)가 이온교환기의 분자구조적 안정성에 영향을 미쳤기 때문으로 사료되었다. 또한 피리디니움 음이온교환막의 전기투석 특성이 semi-pilot 스케일에서 평가되었다.